Hair care compositions comprising hydroxylated triglyceride oligomers

ABSTRACT

Disclosed are hair care compositions, such as shampoos, conditioners and leave on treatments, containing one or more hydroxylated triglyceride oligomers. Also disclosed are methods of using the hair care compositions.

FIELD OF THE INVENTION

The present invention relates to a hair care composition containing ahydroxylated triglyceride oligomer derived from castor oil orlesquerella oil, and methods of using the same.

BACKGROUND OF THE INVENTION

Human hair becomes soiled due to its contact with the surroundingenvironment and from the sebum secreted by the scalp. The soiling ofhair causes it to have a dirty feel and an unattractive appearance.

Shampooing cleans the hair by removing excess soil and sebum. However,shampooing can leave the hair in a wet, tangled, and generallyunmanageable state. Once the hair dries, it is often left in a dry,rough, lusterless, or frizzy condition due to removal of the hair'snatural oils.

A variety of approaches have been developed to alleviate theseafter-shampoo problems. One approach is the application of hair shampooswhich attempt to both cleanse and condition the hair from a singleproduct. Other approaches include the applications of hair conditionerand/or a leave in treatment following shampooing.

In order to provide hair conditioning benefits in a hair care base, awide variety of conditioning actives have been proposed. However,including active levels of conditioning agents in shampoos, conditionersand treatments may result in rheology and stability issues, creatingconsumer trade-offs in cleaning, lather profiles, and weigh-downeffects. Additionally, the rising costs of silicone and thenon-biodegradable nature of silicone have minimized silicone'sdesirability as a conditioning active.

Based on the foregoing, there is a need for a conditioning active whichcan provide conditioning benefits to hair and can replace, or be used incombination with silicone, or other conditioning actives, to maximizethe conditioning activity of hair care compositions. Additionally, thereis a desire to find a conditioning active which can be derived from anatural source, thereby providing a conditioning active derived from arenewable resource. There is also a desire to find a conditioning activethat is both biodegradable and leads to a stable product comprising amicellar surfactant system.

SUMMARY OF THE INVENTION

The present invention is directed to a hair care composition comprising:

-   -   a) from about 0.01% to about 15%, by weight of said hair care        composition, of a hydroxylated triglyceride oligomer comprising:        -   (i.) at least two hydroxylated triglyceride repeating units,            wherein the hydroxylated triglyceride repeating units            comprise one or more hydroxyl groups; and        -   (ii.) at least one fatty acid esterified with at least one            of the hydroxyl groups in the hydroxylated triglyceride            oligomer; and        -   wherein the oligomer has a viscosity of from 1 to 30 Pa·s;            and    -   b) a vehicle having one or more of the following components, by        weight of said hair care composition,        -   (i.) an aqueous carrier;        -   (ii.) from about 5% to about 50% of one or more anionic            surfactants in an aqueous carrier;        -   (ii.) a gel matrix phase in an aqueous carrier comprising,            by weight of said hair care composition:            -   1) from about 0.1% to about 20% of one or more high                melting point fatty compounds;            -   2) from about 0.1% to about 10% of a cationic surfactant                system;        -   (iii.) from about 0.1% to 20% of a nonionic surfactant in an            aqueous carrier;        -   (iv.) from about 20% to about 99.99% of a solvent carrier.

The present invention also is directed to a method for cleansing andconditioning hair with an effective amount of the hair care compositiondescribed above.

These and other features, aspects, and advantages of the presentinvention will become evident to those skilled in the art from a readingof the present disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the structure of castor oil.

FIGS. 2-9 show structures of Materials 1-8, respectively, used ininventive compositions.

FIGS. 10-12 show structures of Materials 9-11, respectively, used incomparative compositions.

DETAILED DESCRIPTION OF THE INVENTION

In all embodiments of the present invention, all percentages are byweight of the total composition, unless specifically stated otherwise.All ratios are weight ratios, unless specifically stated otherwise. Allranges are inclusive and combinable. The number of significant digitsconveys neither a limitation on the indicated amounts nor on theaccuracy of the measurements. All numerical amounts are understood to bemodified by the word “about” unless otherwise specifically indicated.Unless otherwise indicated, all measurements are understood to be madeat 25° C. and at ambient conditions, where “ambient conditions” meansconditions under about one atmosphere of pressure and at about 50%relative humidity. All such weights as they pertain to listedingredients are based on the active level and do not include carriers orby-products that may be included in commercially available materials,unless otherwise specified.

The term “comprising,” as used herein, means that other steps and otheringredients which do not affect the end result can be added. This termencompasses the terms “consisting of” and “consisting essentially of.”The compositions and methods/processes of the present invention cancomprise, consist of, and consist essentially of the elements andlimitations of the invention described herein, as well as any of theadditional or optional ingredients, components, steps, or limitationsdescribed herein.

The terms “include,” “includes,” and “including,” as used herein, aremeant to be non-limiting and are understood to mean “comprise,”“comprises,” and “comprising,” respectively.

The test methods disclosed in the Test Methods Section of the presentapplication should be used to determine the respective values of theparameters of Applicants' inventions.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated. The term “weight percent” may bedenoted as “wt. %” herein.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

A. Hydroxylated Triglyceride Oligimers Derived from Castor Oil orLesquerella Oil

The hair care composition may comprise from about 0.01% to about 15%,alternatively from about 0.1% to about 10%, and alternatively from about0.25% to about 5%, of one or more derivatives of castor oil,specifically oligomers derived from castor oil (ricinoleic triglycerideoligomers) and lesquerella oil (lesquerolic triglyceride oligomers) byweight of said hair care composition. The term “derivatives” means theresulting esters of an esterification reaction of the hydroxyl groupscontained in castor or lesquerella oil, wherein the esters are derivedfrom carboxylic acids or functional carboxylic acids, and the resultingmaterials are nonionic or cationic in nature. The structure of castoroil is shown in FIG. 1 .

Exemplary hydroxylated triglyceride oligomers and their preparationmethods are set forth herein. A hydroxylated triglyceride oligomerrefers to the product obtained when more than one ricinoleictriglyceride is subjected to an esterification reaction. Esterificationis a reaction of an alcohol with an acid to produce an ester and water.When the acid is a diacid, the propagation of the ester linkage mayoccur resulting in oligomerization or polymerization of the hydroxylatedtriglyceride. For example, the structures of Materials 1-5, as shown inFIGS. 2-6 , depict hydroxylated triglyceride oligomers comprisingricinoleic triglyceride and succinic acid. In these structures, theesterification results in the formation of hydroxylated triglycerideoligomers. The molecular weight of the oligomer determined by GelPermeation Chromatography (GPC) using polystyrene as standard may behigher than the molecular weight of the hydroxylated triglyceride fromwhich the oligomer is formed. Each of the bonded hydroxylatedtriglyceride ester molecules may be referred to as a “repeating unit orgroup”. Typically, the number of hydroxylated triglyceride repeat unitsmay range from 2 to about 6. In many embodiments of the invention, thericinoleic triglyceride is further esterified with a hydroxylated fattyacid. Examples of the hydroxylated fatty acid include ricinoleic acidand 12-hydroxy stearic acid. The purpose of the additional hydroxylatedfatty acid ester on ricinoleic triglyceride is twofold. First, thehydroxyl group on the hydroxylated acid ester serves as the reactionsite for the esterification with succinic acid. The resultinghydroxylated triglyceride oligomer has a longer linker containing twohydroxylated fatty acid groups and one succinic group between thericinoleic triglyceride repeating units than the linker of thehydroxylated triglyceride oligomers formed directly by ricinoleictriglyceride and succinic acid. A shorter linker has only succinic groupbetween the ricinoleic triglyceride repeating units. The long linkerexamples of hydroxylated triglyceride oligomers include Material 1,Material 2, Material 3, and Material 4, while an example of short linkeris Material 5. The linker length is thought to affect molecularflexibility of the oligomers. A long linker is likely to reducemolecular steric hindrance, resulting in more extended conformation ofthe hydroxylated triglyceride oligomer than a short linker. Second, theadditional hydroxylated fatty acid ester on ricinoleic triglyceride,which is not used for the reaction with the diacid, can be furtheresterified with fatty acids to extend the ricinoleic group on thehydroxylated triglyceride oligomer. The fatty acids may include stearicacid, oleic acid, 12-hydroxy acid and mixtures thereof. In someembodiments, the materials may comprise some residual non-esterifiedfatty acid, which can form a separate gel-like phase with or in theoligomer. An exemplary material is Material 1. The examples of Material3, Material 4, and Material 5 have oleic acid ester. The example ofMaterial 1 has stearic acid ester. The example of Material 2 has amixture of stearic acid ester of 25 wt % and oleic acid ester of 75 wt%. In some embodiments, the residual fatty acid may remain in thehydroxylated triglyceride oligomer up to 5 wt %.

Exemplary cationic hydroxylated triglyceride oligomers and theirpreparation methods are set forth herein. The cationic hydroxylatedtriglyceride oligomers may have at least one quaternary ammonium group.The quaternary ammonium group may be from a protonated amino group whenformulated in a hair care composition. The cationic hydroxylatedtriglyceride oligomer may comprise from 2 to about 6 quaternary ammoniumgroups, as exemplified by Materials 6-8, as shown in FIGS. 7-9 ,respectively. The quaternary ammonium groups are connected withhydrocarbons such as in Material 8, or with hydroxylated polyethers suchas in Material 6 and Material 7. The quaternary ammonium group in theoligomer may have a counterion, and the counterion may be a chloride ora fatty acid. The fatty acid counterion may be selected from stearicacid, oleic acid, or mixtures thereof. The ricinoleic triglyceride maybe linked to the quaternary ammonium group. The cationic hydroxylatedtriglyceride oligomer may comprise two hydroxylated triglyceriderepeating units such as Material 8, or four hydroxylated triglyceriderepeating units such as in Materials 6 and 7.

Examples of molecular information for some of the Materials are shown inthe table below. The molecular weight was measured via standard GelPermeation Chromatography (GPC), compared to polystyrene standards.

TABLE 1 Material 3 Material 5 Material 1 Material 7 Weight average 710011700 10200 4000 molecular weight (Mw, Dalton) Polydispersity 1.42 2.611.99 1.4 index Wt % of content < 3.9 1.3 1.6 4.6 Mw 1000

In some embodiments, the oligomer may have a viscosity of from about 1to about 30 Pa·s. In other embodiments, the viscosity may be from about2 to about 25 Pa·s.

Comparative examples of Material 9 and Material 10 of hydroxylatedtriglycerides and their preparation methods are set forth herein andshown in FIGS. 10 and 11 , respectively. These examples fail to show theoligomerization of hydroxylated triglyceride, although esterification isachieved with the hydroxyl group on the ricinoleic triglyceride withacetic acid in Material 9 or a fatty acid in Material 10. The viscosityof these examples is below the inventive range of 1 to 30 Pa·s., asshown in Comparative examples A and B.

Another comparative example is Material 11, Crodabond CSA from Croda, asshown in FIG. 12. It is a copolymer of Hydrogenated Castor Oil/SebacicAcid Copolymer, described in detail in Crodabond CSA technicalinformation from Croda and JP2007126371A. Hydrogenated castor oilsignificantly increases the viscosity of the copolymer to above the highend of the inventive range of 30 Pa·s. for hair conditioning, as shownin Comparative example C. No comparative examples of cationichydroxylated triglyceride oligomers were found.

The hair care compositions of the present invention may comprise ahydroxylated triglyceride oligomer and a vehicle. The vehicle maycomprise combinations of additional components that make up a hair carecomposition including, without being limited to, a surfactant,emulsifier, a fatty compound, an aqueous carrier, a solvent carrier, andadditional components.

B. Surfactant and Emulsifier

The hair care composition may comprise a detersive surfactant, whichprovides cleaning performance to the composition. The detersivesurfactant in turn comprises an anionic surfactant, amphoteric orzwitterionic surfactants, or mixtures thereof. Various examples anddescriptions of detersive surfactants are set forth in U.S. Pat. No.6,649,155; U.S. Patent Application Publication No. 2008/0317698; andU.S. Patent Application Publication No. 2008/0206355, which areincorporated herein by reference in their entirety.

The concentration of the detersive surfactant component in the hair carecomposition should be sufficient to provide the desired cleaning andlather performance, and generally ranges from about 2 wt % to about 50wt %, from about 5 wt % to about 30 wt %, from about 8 wt % to about 25wt %, or from about 10 wt % to about 20 wt %. Accordingly, the hair carecomposition may comprise a detersive surfactant in an amount of about 5wt %, about 10 wt %, about 12 wt %, about 15 wt %, about 17 wt %, about18 wt %, or about 20 wt %, for example.

Anionic surfactants suitable for use in the compositions are the alkyland alkyl ether sulfates. Other suitable anionic surfactants are thewater-soluble salts of organic, sulfuric acid reaction products. Stillother suitable anionic surfactants are the reaction products of fattyacids esterified with isethionic acid and neutralized with sodiumhydroxide. Other similar anionic surfactants are described in U.S. Pat.Nos. 2,486,921; 2,486,922; and 2,396,278, which are incorporated hereinby reference in their entirety.

Exemplary anionic surfactants for use in the hair care compositioninclude ammonium lauryl sulfate, ammonium laureth sulfate, triethylaminelauryl sulfate, triethylamine laureth sulfate, triethanolamine laurylsulfate, triethanolamine laureth sulfate, monoethanolamine laurylsulfate, monoethanolamine laureth sulfate, diethanolamine laurylsulfate, diethanolamine laureth sulfate, lauric monoglyceride sodiumsulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium laurylsulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodiumlauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoylsulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroylsulfate, potassium cocoyl sulfate, potassium lauryl sulfate,triethanolamine lauryl sulfate, triethanolamine lauryl sulfate,monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodiumtridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, sodiumcocoyl isethionate and combinations thereof. In a further embodiment,the anionic surfactant is sodium lauryl sulfate or sodium laurethsulfate.

A variety of anionic emulsifiers can be used in the hair carecomposition as described below. The anionic emulsifiers include, by wayof illustrating and not limitation, water-soluble salts of alkylsulfates, alkyl ether sulfates, alkyl isothionates, alkyl carboxylates,alkyl sulfosuccinates, alkyl succinamates, alkyl sulfate salts such assodium dodecyl sulfate, alkyl sarcosinates, alkyl derivatives of proteinhydrolyzates, acyl aspartates, alkyl or alkyl ether or alkylaryl etherphosphate esters, sodium dodecyl sulphate, phospholipids or lecithin, orsoaps, sodium, potassium or ammonium stearate, oleate or palmitate,alkylarylsulfonic acid salts such as sodium dodecylbenzenesulfonate,sodium dialkylsulfosuccinates, dioctyl sulfosuccinate, sodiumdilaurylsulfosuccinate, poly(styrene sulfonate) sodium salt,isobutylene-maleic anhydride copolymer, gum arabic, sodium alginate,carboxymethylcellulose, cellulose sulfate and pectin, poly(styrenesulfonate), isobutylene-maleic anhydride copolymer, gum arabic,carrageenan, sodium alginate, pectic acid, tragacanth gum, almond gumand agar; semi-synthetic polymers such as carboxymethyl cellulose,sulfated cellulose, sulfated methylcellulose, carboxymethyl starch,phosphated starch, lignin sulfonic acid; and synthetic polymers such asmaleic anhydride copolymers (including hydrolyzates thereof),polyacrylic acid, polymethacrylic acid, acrylic acid butyl acrylatecopolymer or crotonic acid homopolymers and copolymers,vinylbenzenesulfonic acid or 2-acrylamido-2-methylpropanesulfonic acidhomopolymers and copolymers, and partial amide or partial ester of suchpolymers and copolymers, carboxymodified polyvinyl alcohol, sulfonicacid-modified polyvinyl alcohol and phosphoric acid-modified polyvinylalcohol, phosphated or sulfated tristyrylphenol ethoxylates.

In addition, anionic emulsifiers that have acrylate functionality mayalso be used in the instant shampoo compositions. Anionic emulsifiersuseful herein include, but aren't limited to: poly(meth)acrylic acid;copolymers of (meth)acrylic acids and its (meth)acrylates with C1-22alkyl, C1-C8 alkyl, butyl; copolymers of (meth)acrylic acids and(meth)acrylamide; Carboxyvinylpolymer; acrylate copolymers such asAcrylate/C10-30 alkyl acrylate crosspolymer, Acrylic acid/vinyl estercopolymer/Acrylates/Vinyl Isodecanoate crosspolymer,Acrylates/Palmeth-25 Acrylate copolymer, Acrylate/Steareth-20 Itaconatecopolymer, and Acrylate/Celeth-20 Itaconate copolymer; Polystyrenesulphonate, copolymers of methacrylic acid and acrylamidomethylpropanesulfonic acid, and copolymers of acrylic acid andacrylamidomethylpropane sulfonic acid; carboxymethycellulose; carboxyguar; copolymers of ethylene and maleic acid; and acrylate siliconepolymer. Neutralizing agents may be included to neutralize the anionicemulsifiers herein. Non-limiting examples of such neutralizing agentsinclude sodium hydroxide, potassium hydroxide, ammonium hydroxide,monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine,aminomethylpropanol, tromethamine, tetrahydroxypropyl ethylenediamine,and mixtures thereof. Commercially available anionic emulsifiersinclude, for example, Carbomer supplied from Noveon under the tradenameCarbopol 981 and Carbopol 980; Acrylates/C10-30 Alkyl AcrylateCrosspolymer having tradenames Pemulen TR-1, Pemulen TR-2, Carbopol1342, Carbopol 1382, and Carbopol ETD 2020, all available from Noveon;sodium carboxymethylcellulose supplied from Hercules as CMC series; andAcrylate copolymer having a tradename Capigel supplied from Seppic. Inanother embodiment, anionic emulsifiers are carboxymethylcelluloses.

Suitable amphoteric or zwitterionic surfactants for use in the hair carecomposition herein include those which are known for use in hair care orother personal care cleansing. Concentrations of such amphotericsurfactants range from about 0.5 wt % to about 20 wt %, and from about 1wt % to about 10 wt %. Non limiting examples of suitable zwitterionic oramphoteric surfactants are described in U.S. Pat. Nos. 5,104,646 and5,106,609, which are incorporated herein by reference in their entirety.

Amphoteric detersive surfactants suitable for use in the hair carecomposition include those surfactants broadly described as derivativesof aliphatic secondary and tertiary amines in which the aliphaticradical can be straight or branched chain and wherein one of thealiphatic substituents contains from about 8 to about 18 carbon atomsand one contains an anionic group such as carboxy, sulfonate, sulfate,phosphate, or phosphonate. Exemplary amphoteric detersive surfactantsfor use in the present hair care composition include cocoamphoacetate,cocoamphodiacetate, lauroamphoacetate, lauroamphodiacetate, and mixturesthereof.

Zwitterionic detersive surfactants suitable for use in the hair carecomposition include those surfactants broadly described as derivativesof aliphatic quaternaryammonium, phosphonium, and sulfonium compounds,in which the aliphatic radicals can be straight or branched chain, andwherein one of the aliphatic substituents contains from about 8 to about18 carbon atoms and one contains an anionic group such as carboxy,sulfonate, sulfate, phosphate or phosphonate. In another embodiment,zwitterionics such as betaines are selected.

Non limiting examples of other anionic, zwitterionic, amphoteric oroptional additional surfactants suitable for use in the compositions aredescribed in McCutcheon's, Emulsifiers and Detergents, 1989 Annual,published by M. C. Publishing Co., and U.S. Pat. Nos. 3,929,678,2,658,072; 2,438,091; 2,528,378, which are incorporated herein byreference in their entirety.

The composition of the present invention may comprise a cationicsurfactant system. The cationic surfactant system can be one cationicsurfactant or a mixture of two or more cationic surfactants. Preferably,the cationic surfactant system is selected from: mono-long alkylquaternized ammonium salt; a combination of mono-long alkyl quaternizedammonium salt and di-long alkyl quaternized ammonium salt; mono-longalkyl amidoamine salt; a combination of mono-long alkyl amidoamine saltand di-long alkyl quaternized ammonium salt, a combination of mono-longalkyl amindoamine salt and mono-long alkyl quaternized ammonium salt.

The cationic surfactant system may be included in the composition at alevel by weight of from about 0.1% to about 10%, preferably from about0.5% to about 8%, more preferably from about 0.8% to about 5%, stillmore preferably from about 1.0% to about 4%.

Mono-Long Alkyl Quaternized Ammonium Salt

The monoalkyl quaternized ammonium salt cationic surfactants usefulherein are those having one long alkyl chain which has from 12 to 30carbon atoms, preferably from 16 to 24 carbon atoms, more preferablyC18-22 alkyl group. The remaining groups attached to nitrogen areindependently selected from an alkyl group of from 1 to about 4 carbonatoms or an alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl oralkylaryl group having up to about 4 carbon atoms.

Mono-long alkyl quaternized ammonium salts useful herein are thosehaving the formula (I):

$\begin{matrix}{\begin{matrix} & & R^{75} & & \\ & & | & & \\R^{76} & — & N^{\oplus} & — & R^{78} \\ & & | & & \\ & & R^{77} & & \end{matrix}X^{\ominus}} & (I)\end{matrix}$

wherein one of R⁷⁵, R⁷⁶, R⁷⁷ and R⁷⁸ is selected from an alkyl group offrom 12 to 30 carbon atoms or an aromatic, alkoxy, polyoxyalkylene,alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 30carbon atoms; the remainder of R⁷⁵, R⁷⁶, R⁷⁷ and R⁷⁸ are independentlyselected from an alkyl group of from 1 to about 4 carbon atoms or analkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylarylgroup having up to about 4 carbon atoms; and X⁻ is a salt-forming anionsuch as those selected from halogen, (e.g. chloride, bromide), acetate,citrate, lactate, glycolate, phosphate, nitrate, sulfonate, sulfate,alkylsulfate, and alkyl sulfonate radicals. The alkyl groups cancontain, in addition to carbon and hydrogen atoms, ether and/or esterlinkages, and other groups such as amino groups. The longer chain alkylgroups, e.g., those of about 12 carbons, or higher, can be saturated orunsaturated. Preferably, one of R⁷⁵, R⁷⁶, R⁷⁷ and R⁷⁸ is selected froman alkyl group of from 12 to 30 carbon atoms, more preferably from 16 to24 carbon atoms, still more preferably from 18 to 22 carbon atoms, evenmore preferably 22 carbon atoms; the remainder of R⁷⁵, R⁷⁶, R⁷⁷ and R⁷⁸are independently selected from CH₃, C₂H₅, C₂H₄OH, and mixtures thereof;and X is selected from the group consisting of Cl, Br, CH₃OSO₃,C₂H₅OSO₃, and mixtures thereof.

Nonlimiting examples of such mono-long alkyl quaternized ammonium saltcationic surfactants include: behenyl trimethyl ammonium salt; stearyltrimethyl ammonium salt; cetyl trimethyl ammonium salt; and hydrogenatedtallow alkyl trimethyl ammonium salt.

Mono-Long Alkyl Amidoamine Salt

Mono-long alkyl amines are also suitable as cationic surfactants.Primary, secondary, and tertiary fatty amines are useful. Particularlyuseful are tertiary amido amines having an alkyl group of from about 12to about 22 carbons. Exemplary tertiary amido amines include:stearamidopropyldimethylamine, stearamidopropyldiethylamine,stearamidoethyldiethylamine, stearamidoethyldimethylamine,palmitamidopropyldimethylamine, palmitamidopropyldiethylamine,palmitamidoethyldiethylamine, palmitamidoethyldimethylamine,behenamidopropyldimethylamine, behenamidopropyldiethylamine,behenamidoethyldiethylamine, behenamidoethyldimethylamine,arachidamidopropyldimethylamine, arachidamidopropyldiethylamine,arachidamidoethyldiethylamine, arachidamidoethyldimethylamine,diethylaminoethylstearamide.

Useful amines in the present invention are disclosed in U.S. Pat. No.4,275,055, Nachtigal, et al. These amines can also be used incombination with acids such as l-glutamic acid, lactic acid,hydrochloric acid, malic acid, succinic acid, acetic acid, fumaric acid,tartaric acid, citric acid, t-glutamic hydrochloride, maleic acid, andmixtures thereof; more preferably l-glutamic acid, lactic acid, citricacid. The amines herein are preferably partially neutralized with any ofthe acids at a molar ratio of the amine to the acid of from about 1:0.3to about 1:2, more preferably from about 1:0.4 to about 1:1.

Di-Long Alkyl Quaternized Ammonium Salt

Di-long alkyl quaternized ammonium salt is preferably combined with amono-long alkyl quaternized ammonium salt or mono-long alkyl amidoaminesalt. It is believed that such combination can provide easy-to rinsefeel, compared to single use of a monoalkyl quaternized ammonium salt ormono-long alkyl amidoamine salt. In such combination with a mono-longalkyl quaternized ammonium salt or mono-long alkyl amidoamine salt, thedi-long alkyl quaternized ammonium salts are used at a level such thatthe wt % of the dialkyl quaternized ammonium salt in the cationicsurfactant system is in the range of preferably from about 10% to about50%, more preferably from about 30% to about 45%.

The dialkyl quaternized ammonium salt cationic surfactants useful hereinare those having two long alkyl chains having 12-30 carbon atoms,preferably 16-24 carbon atoms, more preferably 18-22 carbon atoms. Theremaining groups attached to nitrogen are independently selected from analkyl group of from 1 to about 4 carbon atoms or an alkoxy,polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl grouphaving up to about 4 carbon atoms.

Di-long alkyl quaternized ammonium salts useful herein are those havingthe formula (II):

$\begin{matrix}{\begin{matrix} & & R^{75} & & \\ & & | & & \\R^{76} & — & N^{\oplus} & — & R^{78} \\ & & | & & \\ & & R^{77} & & \end{matrix}X^{\ominus}} & ({II})\end{matrix}$

wherein two of R⁷⁵, R⁷⁶, R⁷⁷ and R⁷⁸ is selected from an alkyl group offrom 12 to 30 carbon atoms or an aromatic, alkoxy, polyoxyalkylene,alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 30carbon atoms; the remainder of R⁷⁵, R⁷⁶, R⁷⁷ and R⁷⁸ are independentlyselected from an alkyl group of from 1 to about 4 carbon atoms or analkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylarylgroup having up to about 4 carbon atoms; and X⁻ is a salt-forming anionsuch as those selected from halogen, (e.g. chloride, bromide), acetate,citrate, lactate, glycolate, phosphate, nitrate, sulfonate, sulfate,alkylsulfate, and alkyl sulfonate radicals. The alkyl groups cancontain, in addition to carbon and hydrogen atoms, ether and/or esterlinkages, and other groups such as amino groups. The longer chain alkylgroups, e.g., those of about 12 carbons, or higher, can be saturated orunsaturated. Preferably, one of R⁷⁵, R⁷⁶, R⁷⁷ and R⁷⁸ is selected froman alkyl group of from 12 to 30 carbon atoms, more preferably from 16 to24 carbon atoms, still more preferably from 18 to 22 carbon atoms, evenmore preferably 22 carbon atoms; the remainder of R⁷⁵, R⁷⁶, R⁷⁷ and R⁷⁸are independently selected from CH₃, C₂H₅, C₂H₄OH, and mixtures thereof;and X is selected from the group consisting of Cl, Br, CH₃OSO₃,C₂H₅OSO₃, and mixtures thereof.

Such dialkyl quaternized ammonium salt cationic surfactants include, forexample, dialkyl (14-18) dimethyl ammonium chloride, ditallow alkyldimethyl ammonium chloride, dihydrogenated tallow alkyl dimethylammonium chloride, distearyl dimethyl ammonium chloride, and dicetyldimethyl ammonium chloride. Such dialkyl quaternized ammonium saltcationic surfactants also include, for example, asymmetric dialkylquaternized ammonium salt cationic surfactants.

The compositions of the present invention may comprise a nonionicsurfactant. Suitable nonionic surfactants for use in the hair carecompositions include, but are not limited to, the non-ionic detersivesurfactant comprises a C₈-C₂₄ alkyl alkoxylated alcohol having anaverage degree of alkoxylation of from 1 to 20, preferably a C₁₀-C₁₈alkyl alkoxylated alcohol having an average degree of alkoxylation offrom 1 to 10, or even a C₂-C₁₈ alkyl alkoxylated alcohol having anaverage degree of alkoxylation of from 1 to 7. Preferably, the non-ionicdetersive surfactant is an ethoxylated alcohol. Preferably, thenon-ionic surfactant comprises an alkyl polyglucoside. The non-ionicdetersive surfactant may even be a predominantly C₁₆ alkyl ethoxylatedalcohol having an average degree of ethoxylation of from 3 to 7.

In an embodiment, the surfactant may be a nonionic surfactant selectedfrom the group consisting of: Cocainide, Cocamide Methyl MEA, CocanideDEA, Cocamide MEA, Cocainide MIPA, Lauramide DEA. Lauramide MEA.Lauramide MIPA. Myristamide DEA. Myristamide MEA. PEG-20 Cocamide MEA,PEG-2 Cocanmide, PEG-3 Cocanide, PEG-4 Cocamide, PEG-5 Cocamide, PEG-6Cocamide, PEG-7 Cocamide. PEG3 Lauramide. PEG-5 Lauramide. PEG3Oleamide, PPG-2 Cocamide, PPG-2 Hydroxyethyl Cocamide, and mixturesthereof.

Suitable nonionic surfactants for use in the hair care compositionsinclude, but are not limited to, polyoxyethylenated alkyl penoils,polyoxyethylenated alcohols, polyoxyethylenated polyoxypropyleneglycols, polyoxyeihylenated hydrogenated castor oil, glyceryl esters ofalkanoic acids, polyglyceryl esters of alkanoic acids, propylene glycolesters of alkanoic acids, sorbitol esters of alkanoic acids,polyoxyethylenated sorbitor esters of alkanoic acids, polyoxyethiyleneglycol esters of alkanoic acids, polyoxyethylenated alkanoic acids,alkanolamides. N-alkylpyrrolidones, alkyl glycosidies, alkylpolyglucosides, alkylamine oxides, and polyoxyethylenated silicones.

C. High Melting Point Fatty Compound

The high melting point fatty compound that is useful herein may have amelting point of 25° C. or higher and may be selected from the groupconsisting of fatty alcohols, fatty acids, fatty alcohol derivatives,fatty acid derivatives, and mixtures thereof. It is understood by theartisan that the compounds disclosed in this section of thespecification can in some instances fall into more than oneclassification, e.g., some fatty alcohol derivatives can also beclassified as fatty acid derivatives. However, a given classification isnot intended to be a limitation on that particular compound, but is doneso for convenience of classification and nomenclature. Further, it isunderstood by the artisan that, depending on the number and position ofdouble bonds, and length and position of the branches, certain compoundshaving certain required carbon atoms may have a melting point of lessthan 25° C. Such compounds of low melting point are not intended to beincluded in this section. Nonlimiting examples of the high melting pointcompounds are found in International Cosmetic Ingredient Dictionary,Fifth Edition, 1993, and CTFA Cosmetic Ingredient Handbook, SecondEdition, 1992. Among a variety of high melting point fatty compounds,fatty alcohols are preferably used in the composition of the presentinvention. The fatty alcohols useful herein are those having from about14 to about 30 carbon atoms, preferably from about 16 to about 22 carbonatoms. These fatty alcohols are saturated and can be straight orbranched chain alcohols. Preferred fatty alcohols include, for example,cetyl alcohol, stearyl alcohol, behenyl alcohol, and mixtures thereof.

High melting point fatty compounds of a single compound of high purityare preferred. Single compounds of pure fatty alcohols selected from thegroup of pure cetyl alcohol, stearyl alcohol, and behenyl alcohol arehighly preferred. By “pure” herein, what is meant is that the compoundhas a purity of at least about 90%, preferably at least about 95%. Thesesingle compounds of high purity provide good rinsability from the hairwhen the consumer rinses off the composition.

The high melting point fatty compound is included in the composition ata level of from about 0.1% to about 20%, preferably from about 1% toabout 15%, more preferably from about 1.5% to about 8% by weight of thecomposition, in view of providing improved conditioning benefits such asslippery feel during the application to wet hair, softness andmoisturized feel on dry hair.

D. Gel Matrix

The compositions of the present invention may comprise a gel matrix. Thegel matrix comprises a cationic surfactant, a high melting point fattycompound, and an aqueous carrier.

The gel matrix is suitable for providing various conditioning benefitssuch as slippery feel during the application to wet hair and softnessand moisturized feel on dry hair. In view of providing the above gelmatrix, the cationic surfactant and the high melting point fattycompound are contained at a level such that the weight ratio of thecationic surfactant to the high melting point fatty compound is in therange of, preferably from about 1:1 to about 1:10, more preferably fromabout 1:1 to about 1:6.

The gel matrix of the hair care composition of the present invention mayinclude an aqueous carrier. Accordingly, the formulations of the presentinvention can be in the form of pourable liquids (under ambientconditions). Such compositions will therefore typically comprise anaqueous carrier, which is present at a level of from about 20 wt % toabout 95 wt %, or even from about 60 wt % to about 85 wt %. The aqueouscarrier may comprise water, or a miscible mixture of water and organicsolvent, and in one aspect may comprise water with minimal or nosignificant concentrations of organic solvent, except as otherwiseincidentally incorporated into the composition as minor ingredients ofother components.

The aqueous carrier useful in the present invention includes water andwater solutions of lower alkyl alcohols and polyhydric alcohols. Thelower alkyl alcohols useful herein are monohydric alcohols having 1 to 6carbons, in one aspect, ethanol and isopropanol. The polyhydric alcoholsuseful herein include propylene glycol, hexylene glycol, glycerin, andpropane diol.

According to embodiments of the present invention, the hair carecompositions may have a pH in the range from about 2 to about 10, at 25°C. In one embodiment, the hair care composition has a pH in the rangefrom about 2 to about 6, which may help to solubilize minerals and redoxmetals already deposited on the hair. Thus, the hair care compositioncan also be effective toward washing out the existing minerals and redoxmetals deposits, which can reduce cuticle distortion and thereby reducecuticle chipping and damage.

E. Aqueous Carrier The hair care compositions can be in the form ofpourable liquids (under ambient conditions). Such compositions willtherefore typically comprise a carrier, which is present at a level offrom about 20 wt % to about 95 wt %, or even from about 60 wt % to about85 wt %. The carrier may comprise water, or a miscible mixture of waterand organic solvent, and in one aspect may comprise water with minimalor no significant concentrations of organic solvent, except as otherwiseincidentally incorporated into the composition as minor ingredients ofother components.

The carrier useful in embodiments of the hair care composition includeswater and water solutions of lower alkyl alcohols and polyhydricalcohols. The lower alkyl alcohols useful herein are monohydric alcoholshaving 1 to 6 carbons, in one aspect, ethanol and isopropanol. Exemplarypolyhydric alcohols useful herein include propylene glycol, hexyleneglycol, glycerin, and propane diol.

F. Solvent Carrier

The composition according to the invention can be formulated in analcoholic or aqueous-alcoholic composition. The hair treatingcomposition can therefore optionally include liquid water-miscible orwater-soluble solvents such as lower alkyl alcohols, e. g. C₁-C₅ alkylmonohydric alcohols, preferably C₂-C₃ alkyl alcohols. Alcohols which maybe present are in particular lower monohydric or polyhydric alcoholshaving 1 to 4 carbon atoms customarily used for cosmetic purposes, suchas preferably ethanol and isopropanol.

The water-soluble polyhydric alcohols usable in the present inventionare also polyhydric alcohols having two or more hydroxyl groups in themolecule. Typical examples of such polyhydric alcohols are dihydricalcohols such as ethylene glycol, propylene glycol, trimethylene glycol,1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol,tetramethylene glycol, 2,3-butylene glycol, pentamethylene glycol,2-butene-1,4-diol, hexylene glycol, octylene glycol; trihydric alcoholssuch as glycerine, trimethylol propane, 1,2,6-hexanetriol and the like;tetrahydric alcohols such as penthaerythritol; pentahydric alcohols suchas xylytol, etc.; hexahydric alcohols such as sorbitol, mannitol;polyhydric alcohol polymers such as diethylene glycol, dipropyleneglycol, polyethylene glycol, polypropylene glycol, tetraethylene glycol,diglycerine, polyethylene glycol, triglycerine, tetraglycerine,polyglycerine; dihydric alcohol alkyl ethers such as ethylene glycolmonomethyl ether, ethylene glycol monoethyl ether, ethylene glycolmonobutyl ether, ethylene glycol monophenyl ether, ethylene glycolmonohexyl ether, ethylene glycol mono-2-methylhexyl ether, ethyleneglycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycolisopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethylether, ethylene glycol dibutyl ether; dihydric alcohol alkyl ethers suchas diethylene glycol monomethyl ether, diethylene glycol monoethylether, diethylene glycol monobutyl ether, diethylene glycol dimethylether, diethylene glycol diethyl ether, diethylene glycol butyl ether,diethylene glycol methyl ethyl ether, triethylene glycol monomethylether, triethylene glycol monoethyl ether, propylene glycol monomethylether, propylene glycol monoethyl ether, propylene glycol monobutylether, propylene glycol isopropyl ether, dipropylene glycol methylether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether;dihydric alcohol ether esters such as ethylene glycol monomethyl etheracetate, ethylene glycol monoethyl ether acetate, ethylene glycolmonobutyl ether acetate, ethylene glycol monophenyl ether acetate,ethylene glycol diadipate, ethylene glycol disuccinate, diethyleneglycol monoethyl ether acetate, diethylene glycol monobutyl etheracetate, propylene glycol monomethyl ether acetate, propylene glycolmonoethyl ether acetate, propylene glycol monopropyl ether acetate,propylene glycol monophenyl ether acetate; glycerine monoalkyl etherssuch as xyl alcohol, selachyl alcohol, batyl alcohol; sugar alcoholssuch as sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol,glucose, fructose, starch sugar, maltose, xylytose, starch sugar reducedalcohol, glysolid, tetrahydrofurfuryl alcohol, POE tetrahydrofurfurylalcohol, POP butyl ether, POP POE butyl ether, tripolyoxypropyleneglycerine ether, POP glycerine ether, POP glycerine ether phosphoricacid, POP POE pentanerythritol ether.

Additional solvent carriers which may be present are cosmeticallyacceptable organic solvents or a mixture of solvents with a boilingpoint below 400° C. Particularly suitable solvent carriers areunbranched or branched hydrocarbons, such as pentane, hexane, isopentaneand cyclic hydrocarbons, such as cyclopentane and cyclohexane. Suitablesolvent carriers also include cyclomethicones, such ascyclopentasiloxane.

G. Additional Components

The hair care composition may further comprise one or more additionalcomponents known for use in hair care or personal care products,provided that the additional components do not otherwise unduly impairproduct stability, aesthetics, or performance. Such optional ingredientsare most typically those described in reference books such as the CTFACosmetic Ingredient Handbook, Second Edition, The Cosmetic, Toiletries,and Fragrance Association, Inc. 1988, 1992. Individual concentrations ofsuch additional components may range from about 0.001 wt % to about 10wt % by weight of the personal care compositions.

Non-limiting examples of additional components for use in the hair carecomposition include conditioning agents (e.g., silicones, hydrocarbonoils, fatty esters, natural oils), natural cationic deposition polymers,synthetic cationic deposition polymers, anti-dandruff agents, particles,suspending agents, paraffinic hydrocarbons, propellants, viscositymodifiers, dyes, non-volatile solvents or diluents (water-soluble andwater-insoluble), pearlescent aids, foam boosters, additionalsurfactants or nonionic cosurfactants, pediculocides, pH adjustingagents, perfumes, preservatives, proteins, skin active agents,sunscreens, UV absorbers, and vitamins.

1. Conditioning Agent

In one embodiment, the hair care compositions comprise one or moreconditioning agents. Conditioning agents include materials that are usedto give a particular conditioning benefit to hair and/or skin. Theconditioning agents useful in the hair care compositions typicallycomprise a water-insoluble, water-dispersible, non-volatile, liquid thatforms emulsified, liquid particles. Suitable conditioning agents for usein the hair care composition are those conditioning agents characterizedgenerally as silicones (e.g., silicone oils, cationic silicones,silicone gums, high refractive silicones, and silicone resins), organicconditioning oils (e.g., hydrocarbon oils, polyolefins, and fattyesters) or combinations thereof, or those conditioning agents whichotherwise form liquid, dispersed particles in the aqueous surfactantmatrix.

One or more conditioning agents are present from about 0.01 wt % toabout 10 wt %, alternatively from about 0.1 wt % to about 8 wt %, andalternatively from about 0.2 wt % to about 4 wt %, by weight of thecomposition.

a. Silicones

The conditioning agent of the hair care composition may be an insolublesilicone conditioning agent. The silicone conditioning agent particlesmay comprise volatile silicone, non-volatile silicone, or combinationsthereof. If volatile silicones are present, it will typically beincidental to their use as a solvent or carrier for commerciallyavailable forms of non-volatile silicone materials ingredients, such assilicone gums and resins. The silicone conditioning agent particles maycomprise a silicone fluid conditioning agent and may also comprise otheringredients, such as a silicone resin to improve silicone fluiddeposition efficiency or enhance glossiness of the hair.

The concentration of the silicone conditioning agent typically rangesfrom about 0.01% to about 10%, by weight of the composition,alternatively from about 0.1% to about 8%, alternatively from about 0.1%to about 5%, and alternatively from about 0.2% to about 3%. Non-limitingexamples of suitable silicone conditioning agents, and optionalsuspending agents for the silicone, are described in U.S. Reissue Pat.No. 34,584, U.S. Pat. Nos. 5,104,646, and 5,106,609, which descriptionsare incorporated herein by reference. The silicone conditioning agentsfor use in the hair care composition may have a viscosity, as measuredat 25 A° C., from about 20 to about 2,000,000 centistokes (“csk”),alternatively from about 1,000 to about 1,800,000 csk, alternativelyfrom about 50,000 to about 1,500,000 csk, and alternatively from about100,000 to about 1,500,000 csk.

The dispersed silicone conditioning agent particles typically have avolume average particle diameter ranging from about 0.01 micrometer toabout 50 micrometer. For small particle application to hair, the volumeaverage particle diameters typically range from about 0.01 micrometer toabout 4 micrometer, alternatively from about 0.01 micrometer to about 2micrometer, and alternatively from about 0.01 micrometer to about 0.5micrometer. For larger particle application to hair, the volume averageparticle diameters typically range from about 5 micrometer to about 125micrometer, alternatively from about 10 micrometer to about 90micrometer, alternatively from about 15 micrometer to about 70micrometer, and alternatively from about 20 micrometer to about 50micrometer.

Background material on silicones including sections discussing siliconefluids, gums, and resins, as well as manufacture of silicones, are foundin Encyclopedia of Polymer Science and Engineering, vol. 15, 2d ed., pp204-308, John Wiley & Sons, Inc. (1989), incorporated herein byreference.

i. Silicone Oils

Silicone fluids include silicone oils, which are flowable siliconematerials having a viscosity, as measured at 25° C., less than 1,000,000csk, alternatively from about 5 csk to about 1,000,000 csk, andalternatively from about 100 csk to about 600,000 csk. Suitable siliconeoils for use in the hair care composition include polyalkyl siloxanes,polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxanecopolymers, and mixtures thereof. Other insoluble, non-volatile siliconefluids having hair conditioning properties may also be used.

Silicone oils include polyalkyl or polyaryl siloxanes which conform tothe following Formula (I):

${\begin{matrix} & & R & & \\ & & | & & \\R & — & {Si} & — & O \\ & & | & & \\ & & R & & \end{matrix}\lbrack\begin{matrix} & R & & \\ & | & & \\— & {Si} & — & O \\ & | & & \\ & R & & \end{matrix}\rbrack}\begin{matrix} & R & & \\ & | & & \\— & \text{?} & — & R \\ & | & & \\{\text{?}} & R & & \end{matrix}$ ?indicates text missing or illegible when filed

wherein R is aliphatic, in some embodiments alkyl, alkenyl, or aryl, Rcan be substituted or unsubstituted, and x is an integer from 1 to about8,000. Suitable R groups for use in the compositions include, but arenot limited to: alkoxy, aryloxy, alkaryl, arylalkyl, arylalkenyl,alkamino, and ether-substituted, hydroxyl-substituted, andhalogen-substituted aliphatic and aryl groups. Suitable R groups alsoinclude cationic amines and quaternary ammonium groups.

Possible alkyl and alkenyl substituents include C₁ to C₅ alkyls andalkenyls, alternatively from C₁ to C₄, and alternatively from C₁ to C₂.The aliphatic portions of other alkyl-, alkenyl-, or alkynyl-containinggroups (such as alkoxy, alkaryl, and alkamino) can be straight orbranched chains, and may be from C₁ to C₅, alternatively from C₁ to C₄,alternatively from C₁ to C₃, and alternatively from C₁ to C₂. Asdiscussed above, the R substituents can also contain aminofunctionalities (e.g. alkamino groups), which can be primary, secondaryor tertiary amines or quaternary ammonium. These include mono-, di- andtri-alkylamino and alkoxyamino groups, wherein the aliphatic portionchain length may be as described herein.

ii. Amino and Cationic Silicones

Cationic silicone fluids suitable for use in the compositions include,but are not limited to, those which conform to the general formula (II):

(R¹)_(a)G_(3−a)-Si—(—OSiG₂)_(n)(—OSiG_(b)(R¹)_(2−b)m)—O—SiG_(3−a)(R¹)_(a)

wherein G is hydrogen, phenyl, hydroxy, or C₁-C₅ alkyl, in someembodiments, methyl; a is 0 or an integer having a value from 1 to 3; bis 0 or 1; n is a number from 0 to 1,999, alternatively from 49 to 499;m is an integer from 1 to 2,000, alternatively from 1 to 10; the sum ofn and m is a number from 1 to 2,000, alternatively from 50 to 500; R¹ isa monovalent radical conforming to the general formula CqH_(2q)L,wherein q is an integer having a value from 2 to 8 and L is selectedfrom the following groups:

—N(R²)CH₂—CH₂—N(R²)₂

—N(R²)₂

—N(R²)₃A⁻

—N(R²)CH₂—CH₂—NR²H₂A⁻

wherein R² is hydrogen, phenyl, benzyl, or a saturated hydrocarbonradical, in some embodiments an alkyl radical from about C₁ to aboutC₂₀, and A⁻ is a halide ion.

In one embodiment, the cationic silicone corresponding to formula (II)is the polymer known as “trimethylsilylamodimethicone”, which is shownbelow in formula (III):

${\begin{matrix}\text{?} & —\end{matrix}\lbrack\begin{matrix} & & \text{?} & \\ & & | & \\O & — & \text{?} & — \\ & & | & \\\text{?} & & \text{?} & \end{matrix}\rbrack}{\begin{matrix} & & & \text{?} & & \\ & & & | & & \\— & O & — & \text{?} & — & \text{?} \\ & & & | & & \\ & & & \text{?} & & \\ & & & | & & \\ & & & \text{?} & & \\ & & & | & & \\ & & & \text{?} & & \\ & & & | & & \\ & & & \text{?} & & \end{matrix}\lbrack\begin{matrix} \\ \\ \\ \\ \\ \\ \\ \\ \\ \\ \\ \\\text{?}\end{matrix}\rbrack}$ ?indicates text missing or illegible when filed

Other silicone cationic polymers which may be used in the hair carecomposition are represented by the general formula (IV):

$\begin{matrix} & & & & \text{?} & & & & & & & & & & & & \\ & & & & | & & & & \text{?} & & & & & & & & \\ & & & & | & & & & | & & & & & & & & \\\text{?} & — & O & — & {Si} & — & O & — & {Si} & — & O & — & \text{?} & — & O & — & \text{?} \\ & & & & | & & & & | & & & & & & & & \\ & & & & \text{?} & & & & \text{?} & & & & & & & & \\ & & & & & & & & & & & & {\text{?}} & & & & \end{matrix}\lbrack\begin{matrix} \\ \\ \\{\lbrack\begin{matrix} \\ \\\text{?}\end{matrix}\rbrack} \\ \\

\end{matrix}\rbrack$ ?indicates text missing or illegible when filed

wherein R³ is a monovalent hydrocarbon radical from C₁ to C₁₈, in someembodiments an alkyl or alkenyl radical, such as methyl; R₄ is ahydrocarbon radical, in some embodiments a C₁ to C₁₈ alkylene radical ora C₁₀ to C₁₈ alkyleneoxy radical, alternatively a C₁ to C₈ alkyleneoxyradical; Q⁻ is a halide ion, in some embodiments chloride; r is anaverage statistical value from 2 to 20, in some embodiments from 2 to 8;s is an average statistical value from 20 to 200, in some embodimentsfrom 20 to 50. One polymer of this class is known as UCARE SILICONE ALE56®, available from Union Carbide.

iii. Silicone Gums

Other silicone fluids suitable for use in the hair care composition arethe insoluble silicone gums. These gums are polyorganosiloxane materialshaving a viscosity, as measured at 25° C., of greater than or equal to1,000,000 csk. Silicone gums are described in U.S. Pat. No. 4,152,416;Noll and Walter, Chemistry and Technology of Silicones, New York:Academic Press (1968); and in General Electric Silicone Rubber ProductData Sheets SE 30, SE 33, SE 54 and SE 76, all of which are incorporatedherein by reference. Specific non-limiting examples of silicone gums foruse in the hair care include polydimethylsiloxane,(polydimethylsiloxane)(methylvinylsiloxane)copolymer,poly(dimethylsiloxane)(diphenyl siloxane)(methylvinylsiloxane)copolymerand mixtures thereof.

iv. High Refractive Index Silicones

Other non-volatile, insoluble silicone fluid conditioning agents thatare suitable for use in the hair care composition are those known as“high refractive index silicones,” having a refractive index of at leastabout 1.46, alternatively at least about 1.48, alternatively at leastabout 1.52, and alternatively at least about 1.55. The refractive indexof the polysiloxane fluid will generally be less than about 1.70,typically less than about 1.60. In this context, polysiloxane “fluid”includes oils as well as gums. The high refractive index polysiloxanefluid includes those represented by general Formula (I) above, as wellas cyclic polysiloxanes such as those represented by Formula (V) below:

$\begin{matrix} & \begin{matrix}R & & \\| & & \\\text{?} & — & \text{?}\end{matrix} \\ & \begin{matrix}\begin{matrix}| \\R\end{matrix}\end{matrix}\end{matrix}$ ?indicates text missing or illegible when filed

wherein R is as defined above, and n is a number from about 3 to about7, alternatively from about 3 to about 5.

The high refractive index polysiloxane fluids contain an amount ofaryl-containing R substituents sufficient to increase the refractiveindex to the desired level, which is described herein. Additionally, Rand n may be selected so that the material is non-volatile.

Aryl-containing substituents include those which contain alicyclic andheterocyclic five and six member aryl rings and those which containfused five or six member rings. The aryl rings themselves can besubstituted or unsubstituted.

Generally, the high refractive index polysiloxane fluids will have adegree of aryl-containing substituents of at least about 15%,alternatively at least about 20%, alternatively at least about 25%,alternatively at least about 35%, and alternatively at least about 50%.Typically, the degree of aryl substitution will be less than about 90%,more generally less than about 85%, alternativelyfrom about 55% to about80%. In some embodiments, the high refractive index polysiloxane fluidshave a combination of phenyl or phenyl derivative substituents, withalkyl substituents, in some embodiments C₁-C₄ alkyl, hydroxy, or C₁-C₄alkylamino (especially —R⁴NHR⁵NH2 wherein each R⁴ and R⁵ independentlyis a C₁-C₃ alkyl, alkenyl, and/or alkoxy).

When high refractive index silicones are used in the hair carecomposition, they may be used in solution with a spreading agent, suchas a silicone resin or a surfactant, to reduce the surface tension by asufficient amount to enhance spreading and thereby enhance theglossiness (subsequent to drying) of hair treated with the compositions.

Silicone fluids suitable for use in the hair care composition aredisclosed in U.S. Pat. Nos. 2,826,551, 3,964,500, 4,364,837, BritishPat. No. 849,433, and Silicon Compounds, Petrarch Systems, Inc. (1984),all of which are incorporated herein by reference.

v. Silicone Resins

Silicone resins may be included in the silicone conditioning agent ofthe hair care composition. These resins are highly cross-linkedpolymeric siloxane systems. The cross-linking is introduced through theincorporation of trifunctional and tetrafunctional silanes withmonofunctional or difunctional, or both, silanes during manufacture ofthe silicone resin.

Silicone materials and silicone resins in particular, can convenientlybe identified according to a shorthand nomenclature system known tothose of ordinary skill in the art as “MDTQ” nomenclature. Under thissystem, the silicone is described according to presence of varioussiloxane monomer units which make up the silicone. Briefly, the symbol Mdenotes the monofunctional unit (CH₃)₃SiO_(0.5); D denotes thedifunctional unit (CH₃)₂SiO; T denotes the trifunctional unit(CH₃)SiO_(1.5); and Q denotes the quadra- or tetra-functional unit SiO₂.Primes of the unit symbols (e.g. M′, D′, T′, and Q′) denote substituentsother than methyl, and must be specifically defined for each occurrence.

Silicone resins for use in the hair care composition may include, butare not limited to MQ, MT, MTQ, MDT and MDTQ resins. Methyl is apossible silicone substituent. In some embodiments, silicone resins areMQ resins, wherein the M:Q ratio is from about 0.5:1.0 to about 1.5:1.0and the average molecular weight of the silicone resin is from about1000 to about 10,000.

The weight ratio of the non-volatile silicone fluid, having refractiveindex below 1.46, to the silicone resin component, when used, may befrom about 4:1 to about 400:1, alternatively from about 9:1 to about200:1, and alternatively from about 19:1 to about 100:1, particularlywhen the silicone fluid component is a polydimethylsiloxane fluid or amixture of polydimethylsiloxane fluid and polydimethylsiloxane gum asdescribed herein. Insofar as the silicone resin forms a part of the samephase in the compositions hereof as the silicone fluid, i.e. theconditioning active, the sum of the fluid and resin should be includedin determining the level of silicone conditioning agent in thecomposition.

b. Organic Conditioning Oils

The conditioning agent of the hair care hair care composition may alsocomprise at least one organic conditioning oil, either alone or incombination with other conditioning agents, such as the siliconesdescribed above.

i. Hydrocarbon Oils

Suitable organic conditioning oils for use as conditioning agents in thehair care composition include, but are not limited to, hydrocarbon oilshaving at least about 10 carbon atoms, such as cyclic hydrocarbons,straight chain aliphatic hydrocarbons (saturated or unsaturated), andbranched chain aliphatic hydrocarbons (saturated or unsaturated),including polymers and mixtures thereof. Straight chain hydrocarbon oilsmay be from about C₁₂ to about C₁₉. Branched chain hydrocarbon oils,including hydrocarbon polymers, typically will contain more than 19carbon atoms.

ii. Polyolefins

Organic conditioning oils for use in the hair care composition can alsoinclude liquid polyolefins, alternatively liquid poly-α-olefins,alternatively hydrogenated liquid poly-α-olefins. Polyolefins for useherein are prepared by polymerization of C₄ to about C₁₄ olefenicmonomers, in some embodiments from about C₆ to about C₁₂.

iii. Fatty Esters

Other suitable organic conditioning oils for use as the conditioningagent in the hair care hair care composition include fatty esters havingat least 10 carbon atoms. These fatty esters include esters withhydrocarbyl chains derived from fatty acids or alcohols. The hydrocarbylradicals of the fatty esters hereof may include or have covalentlybonded thereto other compatible functionalities, such as amides andalkoxy moieties (e.g., ethoxy or ether linkages, etc.).

iv. Fluorinated Conditioning Compounds

Fluorinated compounds suitable for delivering conditioning to hair orskin as organic conditioning oils include perfluoropolyethers,perfluorinated olefins, fluorinebased specialty polymers that may be ina fluid or elastomer form similar to the silicone fluids previouslydescribed, and perfluorinated dimethicones.

v. Fatty Alcohols

Other suitable organic conditioning oils for use in the personal carehair care composition include, but are not limited to, fatty alcoholshaving at least about 10 carbon atoms, alternativelyfrom about 10 toabout 22 carbon atoms, and alternatively from about 12 to about 16carbon atoms.

vi. Alkyl Glucosides and Alkyl Glucoside Derivatives

Suitable organic conditioning oils for use in the personal care haircare composition include, but are not limited to, alkyl glucosides andalkyl glucoside derivatives. Specific non-limiting examples of suitablealkyl glucosides and alkyl glucoside derivatives include Glucam E-10,Glucam E-20, Glucam P-10, and Glucquat 125 commercially available fromAmerchol.

vii. Natural Oils

Natural oils of the type described herein typically are composed oftriglycerides and esters of fatty acids. These fatty acids may be eithersaturated, monounsaturated or polyunsaturated and contain varying chainlengths ranging from C₈ to C₃₀. The most common fatty acids includesaturated fatty acids such as lauric acid (dodecanoic acid), myristicacid (tetradecanoic acid), palmitic acid (hexadecanoic acid), stearicacid (octadecanoic acid), arachidic acid (eicosanoic acid), andlignoceric acid (tetracosanoic acid); unsaturated acids include suchfatty acids as palmitoleic (a C₁₆ acid), and oleic acid (a Cis acid);polyunsaturated acids include such fatty acids as linoleic acid (adi-unsaturated Cis acid), linolenic acid (a tri-unsaturated Cis acid),and arachidonic acid (a tetra-unsubstituted C₂₀ acid). The natural oilsare further comprised of esters of these fatty acids in random placementonto the three sites of the trifunctional glycerine molecule. Differentnatural oils will have different ratios of these fatty acids, and withina given natural oil there is a range of these acids as well depending onsuch factors as where a vegetable or crop is grown, maturity of thevegetable or crop, the weather during the growing season, etc. Thus, itis difficult to have a specific or unique structure for any givennatural oil, but rather a structure is typically based on somestatistical average. For example, soybean oil contains a mixture ofstearic acid, oleic acid, linoleic acid, and linolenic acid in the ratioof 15:24:50:11, and an average number of double bonds of 4.4-4.7 pertriglyceride. One method of quantifying the number of double bonds isthe iodine value (IV) which is defined as the number of grams of iodinethat will react with 100 grams of oil. Therefore, for soybean oil, theaverage iodine value range is from 120-140. Soybean oil may comprisesabout 95% by weight or greater (e.g., 99% weight or greater)triglycerides of fatty acids. Major fatty acids in the polyol esters ofsoybean oil include saturated fatty acids, as a non-limiting example,palmitic acid (hexadecanoic acid) and stearic acid (octadecanoic acid),and unsaturated fatty acids, as a non-limiting example, oleic acid(9-octadecenoic acid), linoleic acid (9,12octadecadienoic acid), andlinolenic acid (9,12,15-octadecatrienoic acid).

In an exemplary embodiment, the vegetable oils include, but not limitedto, canola oil, safflower oil, argan oil, jojoba oil, coconut oil, sheabutter, orange peel wax, tea tree oil, rice bran oil.

c. Other Conditioning Agents

i. Quaternary Ammonium Compounds

Suitable quaternary ammonium compounds for use as conditioning agents inthe personal care hair care composition include, but are not limited to,hydrophilic quaternary ammonium compounds with a long chain substituenthaving a carbonyl moiety, like an amide moiety, or a phosphate estermoiety or a similar hydrophilic moiety.

Examples of useful hydrophilic quaternary ammonium compounds include,but are not limited to, compounds designated in the CTFA CosmeticDictionary as ricinoleamidopropyl trimonium chloride, ricinoleamidotrimonium ethylsulfate, hydroxy stearamidopropyl trimoniummethylsulfateand hydroxy stearamidopropyl trimonium chloride, or combinationsthereof.

ii. Polyethylene Glycols

Additional compounds useful herein as conditioning agents includepolyethylene glycols and polypropylene glycols having a molecular weightof up to about 2,000,000 such as those with CTFA names PEG-200, PEG-400,PEG-600, PEG-1000, PEG-2M, PEG-7M, PEG-14M, PEG-45M and mixturesthereof.

iii. Cationic Polymers

The personal care composition may further comprise a cationic polymer.In combination with a cationic polymer, the hydroxylated triglycerideoligomers in the hair care compositions show enhanced benefits indeposition, wet and dry conditioning and hair feel.

Any known natural or synthetic cationic polymer can be used herein.Examples include those polymers disclosed in U.S. Pat. No. 6,649,155;U.S. Patent Application Publication Nos. 2008/0317698; 2008/0206355; and2006/0099167, which are incorporated herein by reference in theirentirety.

The cationic polymer is included in the composition at a level fromabout 0.01 wt % to about 1 wt %, in one embodiment from about 0.05 wt %to about 1.0 wt %, in another embodiment from about 0.25 wt % to about0.60 wt %, in view of providing the benefits of the hair carecomposition. The ratio of cationic polymer and the hydroxylatedtriglyceride oligomer by weight, in one embodiment range from about1:100 to about 1:1, in another embodiment from 1:10 to about 1:2.

The cationic polymer is a water soluble polymer with a charge densityfrom about 0.5 milliequivalents per gram to about 12 milliequivalentsper gram. The cationic polymer used in the composition has a molecularweight of about 1,000 Daltons to about 100,000,000 Daltons. The cationicpolymer is a low, medium, or high charge density cationic polymer.

These cationic polymers can include at least one of (a) a cationic guarpolymer, (b) a cationic non-guar polymer, (c) a cationic tapiocapolymer, (d) a cationic copolymer of acrylamide monomers and cationicmonomers, (e) a synthetic, non-crosslinked, cationic polymer, whichforms lyotropic liquid crystals upon combination with the detersivesurfactant, and/or (f) cationic hydroxyethyl cellulose. Additionally,the cationic polymer can be a mixture of polymers.

(a) Cationic Guar Polymers

According to one embodiment, the cationic guar polymer has a weightaverage M·Wt. of less than about 1 million g/mol, and has a chargedensity of from about 0.1 meq/g to about 2.5 meq/g. In an embodiment,the cationic guar polymer has a weight average M·Wt. of less than 900thousand g/mol, or from about 150 thousand to about 800 thousand g/mol,or from about 200 thousand to about 700 thousand g/mol, or from about300 thousand to about 700 thousand g/mol, or from about 400 thousand toabout 600 thousand g/mol. from about 150 thousand to about 800 thousandg/mol, or from about 200 thousand to about 700 thousand g/mol, or fromabout 300 thousand to about 700 thousand g/mol, or from about 400thousand to about 600 thousand g/mol. In one embodiment, the cationicguar polymer has a charge density of from about 0.2 to about 2.2 meq/g,or from about 0.3 to about 2.0 meq/g, or from about 0.4 to about 1.8meq/g; or from about 0.5 meq/g to about 1.5 meq/g.

In an embodiment, the composition comprises from about 0.01% to lessthan about 0.6%, or from about 0.04% to about 0.55%, or from about 0.08%to about 0.5%, or from about 0.16% to about 0.5%, or from about 0.2% toabout 0.5%, or from about 0.3% to about 0.5%, or from about 0.4% toabout 0.5%, of cationic guar polymer (a), by total weight of thecomposition.

Suitable cationic guar polymers include cationic guar gum derivatives,such as guar hydroxypropyltrimonium chloride. In an embodiment, thecationic guar polymer is a guar hydroxypropyltrimonium chloride.Specific examples of guar hydroxypropyltrimonium chlorides include theJaguar® series commercially available from Rhone-Poulenc Incorporated,for example Jaguar® C-500, commercially available from Rhodia. Jaguar®C-500 has a charge density of 0.8 meq/g and a M·Wt. of 500,000 g/mole.Another guar hydroxypropyltrimonium chloride with a charge density ofabout 1.1 meq/g and a M·Wt. of about 500,000 g/mole is available fromAshland. A further guar hydroxypropyltrimonium chloride with a chargedensity of about 1.5 meq/g and a M·Wt. of about 500,000 g/mole isavailable from Ashland.

Other suitable polymers include: Hi-Care 1000, which has a chargedensity of about 0.7 meq/g and a M·Wt. of about 600,000 g/mole and isavailable from Rhodia; N-Hance 3269 and N-Hance 3270, which have acharge density of about 0.7 meq/g and a M·Wt. of about 425,000 g/moleand is available from Ashland; AquaCat CG518 has a charge density ofabout 0.9 meq/g and a M·Wt. of about 50,000 g/mole and is available fromAshland. A further non-limiting example is N-Hance 3196 from Ashland.

(b) Cationic Non-Guar Polymers

The shampoo compositions of the present invention comprise agalactomannan polymer derivative having a mannose to galactose ratio ofgreater than 2:1 on a monomer to monomer basis, the galactomannanpolymer derivative selected from the group consisting of a cationicgalactomannan polymer derivative and an amphoteric galactomannan polymerderivative having a net positive charge. As used herein, the term“cationic galactomannan” refers to a galactomannan polymer to which acationic group is added. The term “amphoteric galactomannan” refers to agalactomannan polymer to which a cationic group and an anionic group areadded such that the polymer has a net positive charge.

The galactomannan polymer derivatives for use in the shampoocompositions of the present invention have a molecular weight from about1,000 to about 10,000,000. In one embodiment of the present invention,the galactomannan polymer derivatives have a molecular weight from about5,000 to about 3,000,000. As used herein, the term “molecular weight”refers to the weight average molecular weight. The weight averagemolecular weight may be measured by gel permeation chromatography.

The shampoo compositions of the present invention include galactomannanpolymer derivatives which have a cationic charge density from about 0.9meq/g to about 7 meq/g. In one embodiment of the present invention, thegalactomannan polymer derivatives have a cationinc charge density fromabout 1 meq/g to about 5 meq/g. The degree of substitution of thecationic groups onto the galactomannan structure should be sufficient toprovide the requisite cationic charge density.

(c) Cationically Modified Starch Polymer

The shampoo compositions of the present invention comprise water-solublecationically modified starch polymers. As used herein, the term“cationically modified starch” refers to a starch to which a cationicgroup is added prior to degradation of the starch to a smaller molecularweight, or wherein a cationic group is added after modification of thestarch to achieve a desired molecular weight. The definition of the term“cationically modified starch” also includes amphoterically modifiedstarch. The term “amphoterically modified starch” refers to a starchhydrolysate to which a cationic group and an anionic group are added.

The shampoo compositions of the present invention comprise cationicallymodified starch polymers at a range of about 0.01% to about 10%, andmore preferably from about 0.05% to about 5%, by weight of thecomposition.

Non-limiting examples of these ammonium groups may include substituentssuch as hydroxypropyl trimmonium chloride, trimethylhydroxypropylammonium chloride, dimethylstearylhydroxypropyl ammonium chloride, anddimethyldodecylhydroxypropyl ammonium chloride. See Solarek, D. B.,Cationic Starches in Modified Starches: Properties and Uses, Wurzburg,O. B., Ed., CRC Press, Inc., Boca Raton, Fla. 1986, pp 113-125. Thecationic groups may be added to the starch prior to degradation to asmaller molecular weight or the cationic groups may be added after suchmodification.

The source of starch before chemical modification can be chosen from avariety of sources such as tubers, legumes, cereal, and grains.Non-limiting examples of this source starch may include corn starch,wheat starch, rice starch, waxy corn starch, oat starch, cassaya starch,waxy barley, waxy rice starch, glutenous rice starch, sweet rice starch,amioca, potato starch, tapioca starch, oat starch, sago starch, sweetrice, or mixtures thereof. Tapioca starch is preferred.

In one embodiment of the present invention, cationically modified starchpolymers are selected from degraded cationic maize starch, cationictapioca, cationic potato starch, and mixtures thereof. In anotherembodiment, cationically modified starch polymers are cationic cornstarch and cationic tapioca. Cationic tapioca starch is preferred.

In another embodiment, the cationic deposition polymer is a naturallyderived cationic polymer. The term, “naturally derived cationic polymer”as used herein, refers to cationic deposition polymers which areobtained from natural sources. The natural sources may be polysaccharidepolymers. Therefore, the naturally derived cationic polymer may beselected from the group comprising starch, guar, cellulose, cassia,locust bean, konjac, tara, galactomannan, and tapioca. In a furtherembodiment, cationic deposition polymers are selected from Mirapol® 100S(Rhodia), Jaguar® C17, polyqueaternium-6, cationic tapioca starch(Akzo), polyquaternium-76, and mixtures thereof.

(d) Cationic Copolymer of an Acrylamide Monomer and a Cationic Monomer

According to an embodiment of the present invention, the shampoocomposition comprises a cationic copolymer of an acrylamide monomer anda cationic monomer, wherein the copolymer has a charge density of fromabout 1.0 meq/g to about 3.0 meq/g. In an embodiment, the cationiccopolymer is a synthetic cationic copolymer of acrylamide monomers andcationic monomers.

In an embodiment, the cationic copolymer (b) is AM:TRIQUAT which is acopolymer of acrylamide and1,3-Propanediaminium,N-[2-[[[dimethyl[3-[(2-methyl-1-oxo-2-propenyl)amino]propyl]ammonio]acetyl]amino]ethyl]2-hydroxy-N,N,N′,N′,N′-pentamethyl-,trichloride. AM:TRIQUAT is also known as polyquaternium 76 (PQ76).AM:TRIQUAT may have a charge density of 1.6 meq/g and a M·Wt. of 1.1million g/mol.

In an embodiment, the cationic copolymer is atrimethylammoniopropylmethacrylamide chloride-N-Acrylamide copolymer,which is also known as AM:MAPTAC. AM:MAPTAC may have a charge density ofabout 1.3 meq/g and a M·Wt. of about 1.1 million g/mol. In anembodiment, the cationic copolymer is AM:ATPAC. AM:ATPAC may have acharge density of about 1.8 meq/g and a M·Wt. of about 1.1 milliong/mol.

(e) Cationic Synthetic Polymer

The cationic polymer described herein aids in providing damaged hair,particularly chemically treated hair, with a surrogate hydrophobicF-layer. Lyotropic liquid crystals are formed by combining the syntheticcationic polymers described herein with the aforementioned anionicdetersive surfactant component of the shampoo composition. The syntheticcationic polymer has a relatively high charge density. It should benoted that some synthetic polymers having a relatively high cationiccharge density do not form lyotropic liquid crystals, primarily due totheir abnormal linear charge densities. Such synthetic cationic polymersare described in WO 94/06403 to Reich et al.

The concentration of the cationic polymers ranges about 0.025% to about5%, preferably from about 0.1% to about 3%, more preferably from about0.2% to about 1%, by weight of the shampoo composition.

The cationic polymers have a cationic charge density of from about 2meq/gm to about 7 meq/gm, preferably from about 3 meq/gm to about 7meq/gm, more preferably from about 4 meq/gm to about 7 meq/gm. In someembodiments, the cationic charge density is about 6.2 meq/gm. Thepolymers also have a molecular weight of from about 1,000 to about5,000,000, more preferably from about 10,000 to about 2,000,000, mostpreferably 100,000 to about 2,000,000. where X—=halogen, hydroxide,alkoxide, sulfate or alkylsulfate.

Examples of cationic monomers include aminoalkyl (meth)acrylates,(meth)aminoalkyl (meth)acrylamides; monomers comprising at least onesecondary, tertiary or quaternary amine function, or a heterocyclicgroup containing a nitrogen atom, vinylamine or ethylenimine;diallyldialkyl ammonium salts; their mixtures, their salts, andmacromonomers deriving from therefrom.

Further examples of cationic monomers include dimethylaminoethyl(meth)acrylate, dimethylaminopropyl (meth)acrylate,ditertiobutylaminoethyl (meth)acrylate, dimethylaminomethyl(meth)acrylamide, dimethylaminopropyl (meth)acrylamide, ethylenimine,vinylamine, 2-vinylpyridine, 4-vinylpyridine, trimethylammonium ethyl(meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methylsulphate, dimethylammonium ethyl (meth)acrylate benzyl chloride,4-benzoylbenzyl dimethylammonium ethyl acrylate chloride, trimethylammonium ethyl (meth)acrylamido chloride, trimethyl ammonium propyl(meth)acrylamido chloride, vinylbenzyl trimethyl ammonium chloride,diallyldimethyl ammonium chloride (DADMAC).

Nonlimiting examples of cationic monomers comprise a quaternary ammoniumgroup of formula —NR₃ ⁺, wherein R, which is identical or different,represents a hydrogen atom, an alkyl group comprising 1 to 10 carbonatoms, or a benzyl group, optionally carrying a hydroxyl group, andcomprise an anion (counter-ion). Examples of anions are halides such aschlorides, bromides, sulphates, hydrosulphates, alkylsulphates (forexample comprising 1 to 6 carbon atoms), phosphates, citrates, formates,and acetates.

Nonlimiting examples of cationic monomers include trimethylammoniumethyl (meth)acrylate chloride, trimethylammonium ethyl (meth)acrylatemethyl sulphate, dimethylammonium ethyl (meth)acrylate benzyl chloride,4-benzoylbenzyl dimethylammonium ethyl acrylate chloride, trimethylammonium ethyl (meth)acrylamido chloride, trimethyl ammonium propyl(meth)acrylamido chloride, vinylbenzyl trimethyl ammonium chloride.Nonlimiting examples of cationic monomers include trimethyl ammoniumpropyl (meth)acrylamido chloride.

(f) Cationically Modified Hydroxyethyl Cellulose Polymer

The hair care compositions of the present invention may comprisecationically modified hydroxyethyl cellulose polymers. The cationiccellulosic polymers can further include hydrophobes to adjust polymerhydrophobicity. Non-limiting examples may include polyquaternium-10 ofquaternized hydroxyethyl cellulose, such as UCARE™ Polymer LR-30M,JR-30M and KG-30M and UCARE™ Extreme Polymer from Dow.

In many embodiments, the mixture of the cationic polymers in the haircare composition are binary and ternary. The ratio of the binary mixturein weight ranges from about 1:10 to 10:1. A binary mixture exampleinclude a mixture of DADMAC and UCARE™ Polymer KG-30M with a ratio of1:1.

2. Benefit Agents

In an embodiment, the hair care composition further comprises one ormore additional benefit agents. The benefit agents comprise a materialselected from the group consisting of anti-dandruff agents, vitamins,lipid soluble vitamins, chelants, perfumes, brighteners, enzymes,sensates, attractants, anti-bacterial agents, dyes, pigments, bleaches,and mixtures thereof.

In one aspect said benefit agent may comprise an anti-dandruff agent.Such anti-dandruff particulate should be physically and chemicallycompatible with the components of the composition, and should nototherwise unduly impair product stability, aesthetics or performance.

According to an embodiment, the hair care composition comprises ananti-dandruff active, which may be an anti-dandruff active particulate.In an embodiment, the anti-dandruff active is selected from the groupconsisting of: pyridinethione salts; azoles, such as ketoconazole,econazole, and elubiol; selenium sulphide; particulate sulfur;keratolytic agents such as salicylic acid; and mixtures thereof. In anembodiment, the anti-dandruff particulate is a pyridinethione salt.

Pyridinethione particulates are suitable particulate anti-dandruffactives. In an embodiment, the anti-dandruff active is a1-hydroxy-2-pyridinethione salt and is in particulate form. In anembodiment, the concentration of pyridinethione anti-dandruffparticulate ranges from about 0.01 wt % to about 5 wt %, or from about0.1 wt % to about 3 wt %, or from about 0.1 wt % to about 2 wt %. In anembodiment, the pyridinethione salts are those formed from heavy metalssuch as zinc, tin, cadmium, magnesium, aluminium and zirconium,generally zinc, typically the zinc salt of 1-hydroxy-2-pyridinethione(known as “zinc pyridinethione” or “ZPT”), commonly1-hydroxy-2-pyridinethione salts in platelet particle form. In anembodiment, the 1-hydroxy-2-pyridinethione salts in platelet particleform have an average particle size of up to about 20 microns, or up toabout 5 microns, or up to about 2.5 microns. Salts formed from othercations, such as sodium, may also be suitable. Pyridinethioneanti-dandruff actives are described, for example, in U.S. Pat. Nos.2,809,971; 3,236,733; 3,753,196; 3,761,418; 4,345,080; 4,323,683;4,379,753; and 4,470,982.

In an embodiment, in addition to the anti-dandruff active selected frompolyvalent metal salts of pyrithione, the composition further comprisesone or more anti-fungal and/or anti-microbial actives. In an embodiment,the anti-microbial active is selected from the group consisting of: coaltar, sulfur, fcharcoal, whitfield's ointment, castellani's paint,aluminum chloride, gentian violet, octopirox (piroctone olamine),ciclopirox olamine, undecylenic acid and its metal salts, potassiumpermanganate, selenium sulphide, sodium thiosulfate, propylene glycol,oil of bitter orange, urea preparations, griseofulvin,8-hydroxyquinoline ciloquinol, thiobendazole, thiocarbamates,haloprogin, polyenes, hydroxypyridone, morpholine, benzylamine,allylamines (such as terbinafine), tea tree oil, clove leaf oil,coriander, palmarosa, berberine, thyme red, cinnamon oil, cinnamicaldehyde, citronellic acid, hinokitol, ichthyol pale, Sensiva SC-50,Elestab HP-100, azelaic acid, lyticase, iodopropynyl butylcarbamate(IPBC), isothiazalinones such as octyl isothiazalinone, and azoles, andmixtures thereof. In an embodiment, the anti-microbial is selected fromthe group consisting of: itraconazole, ketoconazole, selenium sulphide,coal tar, and mixtures thereof.

In an embodiment, the azole anti-microbials is an imidazole selectedfrom the group consisting of: benzimidazole, benzothiazole, bifonazole,butaconazole nitrate, climbazole, clotrimazole, croconazole,eberconazole, econazole, elubiol, fenticonazole, fluconazole,flutimazole, isoconazole, ketoconazole, lanoconazole, metronidazole,miconazole, neticonazole, omoconazole, oxiconazole nitrate,sertaconazole, sulconazole nitrate, tioconazole, thiazole, and mixturesthereof, or the azole anti-microbials is a triazole selected from thegroup consisting of: terconazole, itraconazole, and mixtures thereof.When present in the hair care composition, the azole anti-microbialactive is included in an amount of from about 0.01 wt % to about 5 wt %,or from about 0.1 wt % to about 3 wt %, or from about 0.3 wt % to about2 wt %. In an embodiment, the azole anti-microbial active isketoconazole. In an embodiment, the sole anti-microbial active isketoconazole.

Embodiments of the hair care composition may also comprise a combinationof anti-microbial actives. In an embodiment, the combination ofanti-microbial active is selected from the group of combinationsconsisting of: octopirox and zinc pyrithione, pine tar and sulfur,salicylic acid and zinc pyrithione, salicylic acid and elubiol, zincpyrithione and elubiol, zinc pyrithione and climbasole, octopirox andclimbasole, salicylic acid and octopirox, and mixtures thereof.

In an embodiment, the composition comprises an effective amount of azinc-containing layered material. In an embodiment, the compositioncomprises from about 0.001 wt % to about 10 wt %, or from about 0.01 wt% to about 7 wt %, or from about 0.1 wt % to about 5 wt % of azinc-containing layered material, by total weight of the composition.

Zinc-containing layered materials may be those with crystal growthprimarily occurring in two dimensions. It is conventional to describelayer structures as not only those in which all the atoms areincorporated in well-defined layers, but also those in which there areions or molecules between the layers, called gallery ions (A. F. Wells“Structural Inorganic Chemistry” Clarendon Press, 1975). Zinc-containinglayered materials (ZLMs) may have zinc incorporated in the layers and/orbe components of the gallery ions. The following classes of ZLMsrepresent relatively common examples of the general category and are notintended to be limiting as to the broader scope of materials which fitthis definition.

Many ZLMs occur naturally as minerals. In an embodiment, the ZLM isselected from the group consisting of: hydrozincite (zinc carbonatehydroxide), aurichalcite (zinc copper carbonate hydroxide), rosasite(copper zinc carbonate hydroxide), and mixtures thereof. Relatedminerals that are zinc-containing may also be included in thecomposition. Natural ZLMs can also occur wherein anionic layer speciessuch as clay-type minerals (e.g., phyllosilicates) contain ion-exchangedzinc gallery ions. All of these natural materials can also be obtainedsynthetically or formed in situ in a composition or during a productionprocess.

Another common class of ZLMs, which are often, but not always,synthetic, is layered double hydroxides. In an embodiment, the ZLM is alayered double hydroxide conforming to the formula [M²⁺ _(1−x)M³⁺_(x)(OH)₂]^(X+)A^(m−) _(x/m).nH₂O wherein some or all of the divalentions (M²+) are zinc ions (Crepaldi, E L, Pava, P C, Tronto, J, Valim, JB J. Colloid Interfac. Sci. 2002, 248, 429-42).

Yet another class of ZLMs can be prepared called hydroxy double salts(Morioka, H., Tagaya, H., Karasu, M, Kadokawa, J, Chiba, K Inorg. Chem.1999, 38, 4211-6). In an embodiment, the ZLM is a hydroxy double saltconforming to the formula [M²⁺ _(1−x)M²⁺ _(1+x)(OH)_(3(1−y))]⁺A^(n−)_((1=3y)/n).nH₂O where the two metal ions (M²⁺) may be the same ordifferent. If they are the same and represented by zinc, the formulasimplifies to [Zn_(1+x)(OH)₂]^(2x+)2x A⁻.nH₂O. This latter formularepresents (where x=0.4) materials such as zinc hydroxychloride and zinchydroxynitrate. In an embodiment, the ZLM is zinc hydroxychloride and/orzinc hydroxynitrate. These are related to hydrozincite as well wherein adivalent anion replace the monovalent anion. These materials can also beformed in situ in a composition or in or during a production process.

In embodiments having a zinc-containing layered material and apyrithione or polyvalent metal salt of pyrithione, the ratio ofzinc-containing layered material to pyrithione or a polyvalent metalsalt of pyrithione is from about 5:100 to about 10:1, or from about 2:10to about 5:1, or from about 1:2 to about 3:1.

The on-scalp deposition of the anti-dandruff active is at least about 1microgram/cm². The on-scalp deposition of the anti-dandruff active isimportant in view of ensuring that the anti-dandruff active reaches thescalp where it is able to perform its function. In an embodiment, thedeposition of the anti-dandruff active on the scalp is at least about1.5 microgram/cm², or at least about 2.5 microgram/cm², or at leastabout 3 microgram/cm², or at least about 4 microgram/cm², or at leastabout 6 microgram/cm², or at least about 7 microgram/cm², or at leastabout 8 microgram/cm², or at least about 8 microgram/cm², or at leastabout 10 microgram/cm². The on-scalp deposition of the anti-dandruffactive is measured by having the hair of individuals washed with acomposition comprising an anti-dandruff active, for example acomposition pursuant to the present invention, by trained a cosmeticianaccording to a conventional washing protocol. The hair is then parted onan area of the scalp to allow an open-ended glass cylinder to be held onthe surface while an aliquot of an extraction solution is added andagitated prior to recovery and analytical determination of anti-dandruffactive content by conventional methodology, such as HPLC.

Embodiments of the hair care composition may also comprise fatty alcoholgel networks, which have been used for years in cosmetic creams and hairconditioners. These gel networks are formed by combining fatty alcoholsand surfactants in the ratio of about 1:1 to about 40:1 (alternativelyfrom about 2:1 to about 20:1, and alternatively from about 3:1 to about10:1). The formation of a gel network involves heating a dispersion ofthe fatty alcohol in water with the surfactant to a temperature abovethe melting point of the fatty alcohol. During the mixing process, thefatty alcohol melts, allowing the surfactant to partition into the fattyalcohol droplets. The surfactant brings water along with it into thefatty alcohol. This changes the isotropic fatty alcohol drops intoliquid crystalline phase drops. When the mixture is cooled below thechain melt temperature, the liquid crystal phase is converted into asolid crystalline gel network. The gel network contributes a stabilizingbenefit to cosmetic creams and hair conditioners. In addition, theydeliver conditioned feel benefits for hair conditioners.

Thus according to an embodiment, the fatty alcohol is included in thefatty alcohol gel network at a level by weight of from about 0.05 wt %to about 14 wt %. For example, the fatty alcohol may be present in anamount ranging from about 1 wt % to about 10 wt %, and alternativelyfrom about 6 wt % to about 8 wt %.

The fatty alcohols useful herein are those having from about 10 to about40 carbon atoms, from about 12 to about 22 carbon atoms, from about 16to about 22 carbon atoms, or about 16 to about 18 carbon atoms. Thesefatty alcohols can be straight or branched chain alcohols and can besaturated or unsaturated. Nonlimiting examples of fatty alcoholsinclude, cetyl alcohol, stearyl alcohol, behenyl alcohol, and mixturesthereof. Mixtures of cetyl and stearyl alcohol in a ratio of from about20:80 to about 80:20, are suitable.

In some embodiments, the compositions of the present invention may befree of sulfates, free of silicones, mineral oil, dye and/or free ofparabens.

The following is an optional way to prepare a gel network in a shampoo:A vessel is charged with water and the water is heated to about 74° C.Cetyl alcohol, stearyl alcohol, and SLES surfactant are added to theheated water. After incorporation, the resulting mixture is passedthrough a heat exchanger where the mixture is cooled to about 35° C.Upon cooling, the fatty alcohols and surfactant crystallized to form acrystalline gel network. Table 2 provides the components and theirrespective amounts for the gel network composition.

TABLE 2 Gel network components Ingredient Wt. % Water 78.27% CetylAlcohol 4.18% Steary Alcohol 7.52% Sodium laureth-3 sulfate (28% Active)10.00% 5-Chloro-2-methyl-4-isothiazolin-3-one, Kathon CG 0.03%

3. Stabilizing Agents

In an embodiment, the hair care composition further comprises one ormore stabilizing agents. The stabilizing agents comprise a materialselected from the groups consisting of polymeric thickeners, plateletsor crystalline powders. The exemplary stabilizing agents include, butare not limited to, acrylic crosslinked polymers such as acrylatecopolymers having the trade name Rheocare TTA from BASF, ethylene glycoldistearate (EGDS) from Galaxy Surfactants, polyquaternium-10 having atrade name UCARE EP from Dow, and/or hydrogenated castor oil having thetrade name Thixcin R from Elementis Specialties. The concentration ofthe stabilizing agents in the hair care compositions ranges from about0.01% to about 5%.

Examples

The following examples illustrate the present invention. The exemplifiedcompositions can be prepared by conventional formulation and mixingtechniques. It will be appreciated that other modifications of the haircare composition within the skill of those in the hair care formulationart can be undertaken without departing from the spirit and scope ofthis invention. All parts, percentages, and ratios herein are by weightunless otherwise specified. Some components may come from suppliers asdilute solutions. The amount stated reflects the weight percent of theactive material, unless otherwise specified.

TABLE 3 Solvent carrier examples Comparative Inventive A B C D E F G H 1Material 9¹ 10² 11³ 1⁴ 2⁵ 6⁶ 7⁷ 3⁸ 4⁹ Repeat unit M M O O O O O O OSidechain Oleic — Ricinoleic and Oleic FA Stearic Charge — — — — —Cationic — — All exemplary compositions above contain 0.15 wt % ofcomparative or inventive example in Hexane. Key M: Castor oil monomer O:Castor oil oligomer Ingredient Key ¹Material 9, Fatty acid modifiedcastor oil from Momentive ²Material 10, Fatty acid modified castor oilfrom Momentive ³Material 11, Crodabond ™ CSA, Hydrogenated CastorOil/Sebacic Acid Copolymer from Croda ⁴Material 1, poly fatty acid basednonionic castor oil derivative from Momentive ⁵Material 2, poly fattyacid based nonionic castor oil derivative from Momentive ⁶Material 6,poly fatty acid based quaternary ammonium compound from Momentive⁷Material 7, poly fatty acid based quaternary ammonium compound fromMomentive ⁸Material 3, poly fatty acid based nonionic castor oilderivative from Momentive ⁹Material 4, poly fatty acid based nonioniccastor oil derivative from Momentive

TABLE 4 Shampoo examples Comparative Inventive J K L M N O P Q R S T UWater¹ q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s.Sodium Lauroyl 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0Sarcosinate² Sodium Cocoyl 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.06.0 Isethionate³ Lauramidopropyl 9.7 9.7 9.7 9.7 9.7 9.7 9.7 9.7 9.7 9.79.7 9.7 Betaine⁴ Polyquaternium- 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 10LR30M⁵ Polyquaternium- 0.25 0.25 0.25 10 JR30M⁶ Acrylates 0.7 0.7 0.70.7 0.7 0.7 0.7 0.7 0.7 copolymer⁷ EGDS⁸ 2.2 2.2 2.2 Material 7⁹ 1.0 0.50.25 1.0 Material 5¹⁰ 1.0 1.0 Material 3¹¹ 1.0 1.0 Material 6¹² 1.0Material 1¹³ 1.0 Material 11¹⁴ 1.0 Fragrance, Up to Up to 5% Up to Up toUp to Up to Up to Up to Up to Up to Up to Up to preservatives, pH, 5% 5%5% 5% 5% 5% 5% 5% 5% 5% 5% viscosity adjustment Ingredient Key ¹Water,DI water from Misty Mountain Spring water ²Sodium Lauroyl Sarcosinate,SP Crodasinic LS30/NP MBAL-LQ-(RB) from Croda ³Sodium CocoylIsethionate, PUREACT I-85 E-HA Flakes from innospec ⁴LauramidopropylBetaine, Mackam DAB ULS from Salvay USA Inc. ⁵Polyquaternium-10, UCARE ™Polymer LR-30M from Amerchol ⁶Polyquaternium-10, UCARE ™ Polymer JR-30Mfrom Amerchol ⁷Acrylates copolymer, Rheocare TTA from BASF ⁸EGDS,Ethylene glycol distearate from Galaxy Surfactants ⁹Material 7, polyfatty acid based quaternary ammonium compound from Momentive ¹⁰Material5, poly fatty acid based nonionic castor oil derivative from Momentive¹¹Material 3, poly fatty acid based nonionic castor oil derivative fromMomentive ¹²Material 6, poly fatty acid based quaternary ammoniumcompound from Momentive ¹³Material 1, poly fatty acid based nonioniccastor oil derivative from Momentive ¹⁴Material 11, Crodabond ™ CSA,Hydrogenated Castor Oil/Sebacic Acid Copolymer from Croda

TABLE 5 Rinse off conditioner Comparative Inventive V W X Y Z AA BB CCEE Water¹ q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. Behentrimonium3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Methosulfate/Isopropyl alcohol²(BTMS) Cetyl Alcohol³ 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 Steary1Alcohol⁴ 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 Material 1⁵ 1.0 2.0 4.0 1.0Material 7⁶ 1.0 Material 5⁷ 1.0 Material 3⁸ 1.0 Material 11⁹ 1.0 2.0Aminosilicone¹⁰ 1.0 Fragrance, preservatives, pH, Up to 5% Up to 5% Upto Up to Up to Up to Up to Up to Up to viscosity adjustment 5% 5% 5% 5%5% 5% 5% Ingredient Key ¹Water, DI water from Misty Mountain Springwater ²Behentrimonium Methosulfate/Isopropyl alcohol (BTMS) ³CetylAlcohol, CO-1698PT from P&G Chemicals ⁴Stearyl Alcohol, CO-1899 from P&GChemicals ⁵Material 1, poly fatty acid based nonionic castor oilderivative from Momentive ⁶Material 7, poly fatty acid based quaternaryammonium compound from Momentive ⁷Material 5, poly fatty acid basednonionic castor oil derivative from Momentive ⁸Material 3, poly fattyacid based nonionic castor oil derivative from Momentive ⁹Material 11,Crodabond ™ CSA, Hydrogenated Castor Oil/Sebacic Acid Copolymer fromCroda ¹⁰Y-14945 from Momentive

TABLE 6 Leave-on conditioner examples Comparative Inventive FF GG HH IIJJ KK LL Water purified¹ q.s. q.s. q.s. q.s. q.s. q.s. q.s.Hydoxyethylcellulose² 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Behenamidopropy1 0.90.9 0.9 0.9 0.9 0.9 0.9 Dimethylamine³ Cetyl Alcohol⁴ 0.8 0.8 0.8 0.80.8 0.8 0.8 Stearyl Alcohol⁵ 0.5 0.5 0.5 0.5 0.5 0.5 0.5 GlycerylStearate⁶ 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Hexanediol and Caprylyl 0.4 0.40.4 0.4 0.4 0.4 0.4 Glycol⁷ Material 1⁸ 2.0 1.0 0.5 0.5 Material 7⁹ 1.0Aminosilicone¹⁰ 0.5 Material 11¹¹ 0.5 1.0 Fragrance, Up to 5% Up to 5%Up to Up to Up to Up to Up to preservatives, pH, 5% 5% 5% 5% 5%viscosity adjustment Ingredient Key ¹Water, DI water from Misty MountainSpring water ²Hydroxy Cellulose, Natrosol ™ 250HHR CS from Ashland³INCROMINE ™ BD-PA-(MH) from Croda ⁴Stearamidopropyl Dimethylamine(HA162), SP POLAWAX NF MBAL-PA-(RB) from Croda ⁵Cetyl Alcohol, CO-1698PTfrom P&G Chemicals ⁶Stearyl Alcohol, CO-1899 from P&G Chemicals⁷Symdiol ® 68 from Symrise ⁸Material 1, poly fatty acid based nonioniccastor oil derivative from Momentive ⁹Material 7, poly fatty acid basedquaternary ammonium compound from Momentive ¹⁰Aminosilicone, Y-14945from Momentive ¹¹Material 11, Crodabond ™ CSA, Hydrogenated CastorOil/Sebacic Acid Copolymer from Croda

TABLE 7 Leave on conditioner formula Comparative Inventive MM NN OO PPQQ SS TT Water purified¹ q.s. q.s. q.s. q.s. q.s. q.s. q.s. HydroxyCellulose² 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Polyox WSR N-10 PEG 2M³ 0.27 0.270.27 0.27 0.27 0.27 0.27 Quaternium-18⁴ 0.4 0.4 0.4 0.4 0.4 0.4 0.4Stearamidopropy1 0.54 0.54 0.54 0.54 0.54 0.54 0.54 Dimethylamine⁵Cetearyl Alcohol & Polysorbate 0.27 0.27 0.27 0.27 0.27 0.27 0.27 60⁵Cetyl Alcohol⁶ 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Steary1 Alcohol⁷ 0.35 0.350.35 0.35 0.35 0.35 0.35 Glyceryl Stearate⁸ 0.14 0.14 0.14 0.14 0.140.14 0.14 Oley Alcohol⁹ 0.14 0.14 0.14 0.14 0.14 0.14 0.14 Material 1¹⁰2.0 1.0 0.5 0.5 Material 7¹¹ 1.0 Aminosilicone¹² 0.5 Crodabond¹³ 0.5 1.0Preservatives, pH, viscosity Up to 5% Up to 5% Up to Up to Up to Up toUp to adjustment 5% 5% 5% 5% 5% Ingredient Key ¹Water, DI water fromMisty Mountain Spring water ²Hydroxy Cellulose, Natrosol ™ 250HHR CSfrom Ashland ³Polyox WSR N-10 PEG 2M, from Amerchol ⁴Quaternium-18,VARISOFT 442 100 P from Evonik ⁵Stearamidopropyl Dimethylamine (HA162),SP POLAWAX NF MBAL-PA-(RB) from Croda ⁶Cetyl Alcohol, CO-1698PT from P&GChemicals ⁷Stearyl Alcohol, CO-1899 from P&G Chemicals ⁸GlycerylStearate, HALLSTAR ® GMS PURE from Hallstar ⁹Oley Alcohol, HD-Ocenol ®90/95 V from BASF ⁸Material 1, poly fatty acid based nonionic castor oilderivative from Momentive ⁹Material 7, poly fatty acid based quaternaryammonium compound from Momentive ¹⁰Aminosilicone, Y-14945 from Momentive¹¹Crodabond ™ CSA, Hydrogenated Castor Oil/Sebacic Acid Copolymer fromCroda

TABLE 8 Dual phase leave on treatment formula Comparative Inventive UUVV WW XX Phase A-Water Phase Water Purified¹ q.s q.s q.s q.sPolyimide-1² 4.0 4.0 4.0 4.0 Polysorbate 20³ 0.5 0.5 0.5 0.5Polyquaterium-6⁴ 0.6 0.6 0.6 0.6 Preservatives, pH, Up to 5% Up to 5% Upto 5% Up to 5% viscosity adjustment Phase B-Oil phase Isododecane⁵ 25.025.0 25.0 25.0 Diisopropyl Adipate⁶ 5.0 5.0 5.0 5.0 Crodaband⁷ 2.0 — — —Material 7⁸ — 2.0 — — Material 1⁹ — — 2.0 — Material 5¹⁰ — — — 2.0Ingredient Key ¹Water, DI water from Misty Mountain Spring water²Polyimide-1, AQUAFLEX XL-30 from Ashland ³Polysorbate 20, TWEEN ™80-LQ-(AP) from Croda ⁴Polyquaterium-6, Genamin PDAC from Clariant⁵Isododecane, Permethyl 99A from Presperse ⁶Diisopropyl Adipate,SCHERCEMOL ™ DIA ESTER from Lubrizol ⁷Crodabond ™ CSA, HydrogenatedCastor Oil/Sebacic Acid Copolymer from Croda ⁸Material 7, poly fattyacid based quaternary ammonium compound from Momentive ⁹Material 1, polyfatty acid based nonionic castor oil derivative from Momentive¹⁰Material 5, poly fatty acid based nonionic castor oil derivative fromMomentive

The hair care composition may be presented in typical hair careformulations. They may be in the form of solutions, dispersion,emulsions, powders, talcs, encapsulated spheres, spongers, solid dosageforms, foams, and other delivery mechanisms. The compositions of theembodiments of the present invention may be hair tonics, leave-on hairproducts such as treatment and styling products, rinse-off hair productssuch as shampoos, and any other form that may be applied to hair.

According to one embodiment, the hair care compositions may be providedin the form of a porous, dissolvable solid structure, such as thosedisclosed in U.S. Patent Application Publication Nos. 2009/0232873; and2010/0179083, which are incorporated herein by reference in theirentirety. As described in these references, such dissolvable solidstructure embodiments will typically have a water content well below atleast about 20% aqueous carrier element of certain embodiments describedabove. In a solid substrate, the weight percentage of the hydroxylatedtriglyceride oligomer in the dissolvable solid structure is from about 5to about 60, more preferably from about 10 to 40.

The hair care compositions are generally prepared by conventionalmethods such as those known in the art of making the compositions. Suchmethods typically involve mixing of the ingredients in one or more stepsto a relatively uniform state, with or without heating, cooling,application of vacuum, and the like. The compositions are prepared suchas to optimize stability (physical stability, chemical stability,photostability) and/or delivery of the active materials. The hair carecomposition may be in a single phase or a single product, or the haircare composition may be in a separate phases or separate products. Iftwo products are used, the products may be used together, at the sametime or sequentially. Sequential use may occur in a short period oftime, such as immediately after the use of one product, or it may occurover a period of hours or days.

The hydroxylated triglyceride oligomers in the hair care composition canbe dispersed as discrete particles or dissolved in a liquid carrier, aswell as mixed in a solid substrate. The particle size of the discreteparticles ranges from about 0.01 μm to about 50 μm, more preferably fromabout 0.05 μm to about 30 am. The discrete particles can bepre-emulsified prior to the addition to the hair care compositions. Thepre-emulsions include cationic, nonionic, and anionic emulsions withemulsifiers described in G. Additional Components. The particle size ofthe pre-emulsions range is targeted to achieve the particle sizes in thehair care compositions. The ratio of emulsifier and hydroxylatedtriglyceride oligomer by weight in the pre-emulsion range from about0.01 to about 1.0, more preferably from about 0.04 to about 0.4. The pHof the hair care composition is from about 3 to about 8, more preferablyfrom about 4.5 to 7.

Test Methods

It is understood that the test methods that are disclosed in the TestMethods Section of the present application should be used to determinethe respective values of the parameters of Applicants' invention as suchinvention is described and claimed herein.

Viscosity Measurement

The viscosity properties of the hydroxylated triglyceride oligomer andcomparative compound are measured on a stress-controlled rheometer, suchas the TA Discovery HR-3 hybrid rheometer by TA Instrument, using 40millimeter stainless steel parallel plates with 1 millimeter gap. About1 mL of a sample is placed onto the lower plate. The excess material istrimmed using a plastic flat edge ensuring that material is not shearedby movements of the plates. The conditioning step is operated with asoak time of 10.0 second at 25° C. Preshear rate is set at 10 l/s withduration of 10.0 second. The flow-sweep step is run logarithmicallybetween 0.01 and 1000 l/s of shear rate. Data is collected at 10points/decade in log mode. Viscosity (Pa·s.) at shear rate of 1 l/s isused.

Leave on Treatment Protocol

A moderately oxidatively-damaged Caucasian hair switch with weight of 4g and length of 8 inches is first washed with a clarifying shampoo (seeshampoo washing protocol below) and allowed to air dry for 24 hours. Anamount of 500 ppm of a hydroxylated triglyceride oligomer or acomparative example formulated in a carrier is thoroughly spread on thehair switch. The treatment is repeated to two additional switches. Thetreated hair switches are allowed to dry and equilibrate overnight undercontrolled temperature and relative humidity conditions (27° C. and 50%RH).

Shampoo Treatment

A moderately oxidatively-damaged Caucasian hair switch with weight of 4g and length of 8 inches is first wetted with warm water for 30 seconds.An amount of 0.10 g of shampoo per gram of a hair switch is spread via asyringe onto separate hair switch. Each application consists of addingthe shampoo to the hair, milking for 30 seconds followed by rinsing for30 seconds. The treatment is repeated to two additional switches. Thetreated hair switches are allowed to dry and equilibrate overnight undercontrolled temperature and relative humidity conditions (27° C. and 50%RH).

Rinse Off Conditioner Treatment

A moderately oxidatively-damaged Caucasian hair switch with weight of 4g and length of 8 inches is first washed with a clarifying shampoo (seeshampoo washing protocol above). After rinseing, an amount of 0.10 g ofconditioner per gram of a hair switch is spread via a syringe onto thehair switch. Each application consists of adding the conditioner to thehair, milking for 30 seconds followed by rinsing for 30 seconds. Thetreatment is repeated to two additional switches. The treated hairswitches are allowed to dry and equilabrited overnight under controlledtemperature and relative humidity conditions (27° C. and 50% RH).

Dry Combing Tests

This combing test determines the amount of friction on the hair providedby the hair care composition as measured by the force required to move acomb through a moderately oxidatively-damaged Caucasian hair switch withweight of 4 g and length of 8 inches. This method emulates the motion ofcombing hair from the root to tip of the treated hair switch. Theoperator ranks and balances the 4 g, 8 in. hair switches for base linecondition by using an Instron machine. The operator then applies ameasured amount of the hair care composition to a hair switch (0.1 g/ghair), distributes the product evenly through the switch, and rinses asper the protocol. Wet switches are evaluated for friction and thenallowed to dry overnight and evaluated the next day for friction forceusing the Instron machine. Each test product is applied to a total of 3switches. The data is then analyzed using standard statistical methods.The combing force is measured for each switch and an average for thethree switches is calculated. Lower friction forces are better for hairdetangling.

Shampoo In-Lab Screening

A moderately oxidatively-damaged Caucasian hair switch with weight of 20g and length of 10 inches is washed by an expert panelist (see shampoowashing protocol above). The expert panelist gives a score of 0-5 forwet and dry attributes. Two additional expert panelists repeat theprotocol by treating a separate hair switch. The score is the averagefrom three expert panelists. A control treatment without thehydroxylated triglyceride oligomer or exemplary comparative compound isalso tested. Expert evaluation scores are calculated with the formulabelow. Higher scores are better.

Expert evaluation scores=(average score−control score)*100

Comparative Data

Using the abovementioned test protocols, the wet and dry conditioningbenefits of selected formulations were measured. The data in Table 9 andTable 10 reflect improved dry conditioning benefit provided by leave ontreatment compositions containing the hydroxylated triglycerideoligomers described herein. Data in Table 11 demonstrate that thedescribed hydroxylated triglyceride oligomers provided wet and dryconditioning improvements in sulfate free shampoo formulations versuscomparative examples. The data in Table 12 show that the describedhydroxylated triglyceride oligomers provide significantly lower hairfriction in dry conditioning in rinse off conditioners versuscomparative examples.

TABLE 9 Comparative Inventive A B C D E F G H I Material 9 10 11 1 2 6 73 4 Viscosity, Pa · s @ 1 s⁻¹ 0.3 0.6 48.5 5.0 2.8 15.1 1.9 2.2 2.8Combing force, mean 243 225 173 120 141 136 122 117 120 (grams-force)Standard error, gf 38 34 23 13 18 20 16 15 20

TABLE 10 Comparative GG Inventive II Mean Standard error Mean Standarderror (grams- (grams- (grams- (grams- force) force) force) force) Dryfriction at tip 55 1.8 43 1.8 Dry friction in mid 14.9 0.23 12.7 0.21

TABLE 11 Comparative Inventive Expert evaluation scores K L Q R Ease oflathering −13 88 13 25 Wet moisturized/soft feel 113 163 138 150 Dryease of combing (body) 13 100 113 50 Dry ease of combing (tip) 100 163138 125 Dry smooth feel (body) 38 38 125 100 Dry smooth feel (tip) 50 63113 75 Dry clean feel 25 50 38 38

TABLE 12 Comparative V Inventive X Mean Standard error Mean Standarderror (grams- (grams- (grams- (grams- force) force) force) force) Dryfriction at tip 59 2.7 52 2.1 Dry friction in mid 11.7 0.14 8.0 0.34

Examples/Combinations

A. A hair care composition comprising:

a) from about 0.01% to about 15%, by weight of said hair carecomposition, of a hydroxylated triglyceride oligomer comprising:

(i.) at least two hydroxylated triglyceride repeating units, wherein thehydroxylated triglyceride repeating units comprise one or more hydroxylgroups; and

(ii.) at least one fatty acid esterified with at least one of thehydroxyl groups in the hydroxylated triglyceride oligomer and

wherein the oligomer has a viscosity of from 1 to 30 Pa·s; and

b) a vehicle having one or more of the following components, by weightof said hair care composition,

(i.) an aqueous carrier;

(ii.) from about 5% to about 50% of one or more anionic surfactants inan aqueous carrier;

(ii.) a gel matrix phase in an aqueous carrier comprising, by weight ofsaid hair care composition:

-   -   1) from about 0.1% to about 20% of one or more high melting        point fatty compounds;    -   2) from about 0.1% to about 10% of a cationic surfactant system;

(iii.) from about 0.1% to 20% of a nonionic surfactant in an aqueouscarrier;

(iv.) from about 20% to about 99.99% of solvent carrier.

B. The composition of paragraph A, wherein the hydroxylated triglycerideoligomer comprises ricinoleic or lesquerolic triglyceride.C. The composition of any one of paragraphs A or B, wherein the oligomerfurther comprises at least one quaternary ammonium group.D. The composition of any one of paragraphs A to C, wherein thehydroxylated triglyceride oligomer has repeating units of from about 2to about 6.E. The composition of any one of paragraphs A to D, wherein the at leastone fatty acid is esterified with each hydroxyl group in thehydroxylated triglyceride oligomer.F. The composition of any one of paragraphs A to E, wherein the fattyacid esters of the hydroxylated triglyceride oligomer are esterifiedwith fatty acids selected from the group consisting of ricinoleic acid,oleic acid, stearic acid, 12-hydroxy stearic acid and mixtures thereof.G. The composition of paragraph A, wherein the hydroxylated triglycerideoligomer is oligomerized with a diacid.H. The composition of paragraph G, wherein the diacid contains fourcarbons.I. The composition of any one of paragraphs A to H, wherein the fattyacid esters of the hydroxylated triglyceride oligomer have a terminalester of oleic acid or stearic acid.J. The composition of paragraph C, wherein at least one of thequaternary ammonium groups is from a protonated amino group in thehydroxylated triglyceride oligomer.K. The composition of paragraph C, wherein the oligomer comprises from 2to about 6 quaternary ammonium groups.L. The composition of paragraph C, wherein the quaternary ammonium groupin the oligomer has a counter ion, and the counter ion is chloride or afatty acid.M. The composition of paragraph L, wherein the counter ion of thequaternary ammonium group in the hydroxylated triglyceride oligomer isstearic acid or oleic acid.N. The composition of paragraph C, wherein the quaternary ammoniumgroups are connected with hydrocarbon and polyether linkages.O. The composition of paragraph N, wherein all the hydroxylatedtriglyceride repeating units are linked to the quaternary ammoniumgroup.P. The composition of any one of paragraphs A to O, wherein theviscosity of the hydroxylated triglyceride oligomer is about from 2 toabout 25 Pa·s.Q. The composition of any one of paragraphs A to P, wherein thesurfactant is a sulfate-free surfactant.R. The composition of any one of paragraphs A to P, wherein the solventcarrier is a hydrocarbon or an alcohol.S. The composition of any one of paragraphs A to R, wherein thecomposition is silicone-free.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application, is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests,or discloses any such invention. Further, to the extent that any meaningor definition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A hair care composition comprising: a) from about0.01% to about 15%, by weight of said hair care composition, of ahydroxylated triglyceride oligomer comprising: (i.) at least twohydroxylated triglyceride repeating units, wherein the hydroxylatedtriglyceride repeating units comprise one or more hydroxyl groups; and(ii.) at least one fatty acid esterified with at least one of thehydroxyl groups in the hydroxylated triglyceride oligomer and whereinthe oligomer has a viscosity of from 1 to 30 Pa·s; and b) a vehiclehaving one or more of the following components, by weight of said haircare composition, (i.) an aqueous carrier; (ii.) from about 5% to about50% of one or more anionic surfactants in an aqueous carrier; (ii.) agel matrix phase in an aqueous carrier comprising, by weight of saidhair care composition: 1) from about 0.1% to about 20% of one or morehigh melting point fatty compounds; 2) from about 0.1% to about 10% of acationic surfactant system; (iii.) from about 0.1% to 20% of a nonionicsurfactant in an aqueous carrier; (iv.) from about 20% to about 99.99%of solvent carrier.
 2. The composition of claim 1, wherein thehydroxylated triglyceride oligomer comprises ricinoleic or lesquerolictriglyceride.
 3. The composition of claim 1, wherein the oligomerfurther comprises at least one quaternary ammonium group.
 4. The haircare composition of claim 1, wherein the hydroxylated triglycerideoligomer has repeating units of from about 2 to about
 6. 5. The haircare composition of claim 1, wherein the at least one fatty acid isesterified with each hydroxyl group in the hydroxylated triglycerideoligomer.
 6. The hair care composition of claim 1, wherein the fattyacid esters of the hydroxylated triglyceride oligomer are esterifiedwith fatty acids selected from the group consisting of ricinoleic acid,oleic acid, stearic acid, 12-hydroxy stearic acid and mixtures thereof.7. The hair care composition of claim 1, wherein the hydroxylatedtriglyceride oligomer is oligomerized with a diacid.
 8. The hair carecomposition of claim 7, wherein the diacid contains four carbons.
 9. Thehair care composition of claim 1, wherein the fatty acid esters of thehydroxylated triglyceride oligomer have a terminal ester of oleic acidor stearic acid.
 10. The hair care composition of claim 3, wherein atleast one of the quaternary ammonium groups is from a protonated aminogroup in the hydroxylated triglyceride oligomer.
 11. The hair carecomposition of claim 3, wherein the oligomer comprises from 2 to about 6quaternary ammonium groups.
 12. The hair care composition of claim 3,wherein the quaternary ammonium group in the oligomer has a counter ion,and the counter ion is chloride or a fatty acid.
 13. The hair carecomposition of claim 12, wherein the counter ion of the quaternaryammonium group in the hydroxylated triglyceride oligomer is stearic acidor oleic acid.
 14. The hair care composition of claim 3, wherein thequaternary ammonium groups are connected with hydrocarbon and polyetherlinkages.
 15. The hair care composition of claim 14, wherein all thehydroxylated triglyceride repeating units are linked to the quaternaryammonium group.
 16. The hair care composition of claim 1, wherein theviscosity of the hydroxylated triglyceride oligomer is about from 2 toabout 25 Pa·s.
 17. The hair care composition of claim 1, wherein thesurfactant is a sulfate-free surfactant.
 18. The hair care compositionof claim 1, wherein the solvent carrier is a hydrocarbon or an alcohol.19. The hair care composition of claim 1, wherein the composition issilicone-free.